JP5466374B2 - Method for producing unsaturated (poly) alkylene glycol ether monomer and method for producing polymer having (poly) alkylene glycol chain - Google Patents

Description

The present invention relates to a method for producing an unsaturated (poly) alkylene glycol ether monomer and a method for producing a polymer having a (poly) alkylene glycol chain. More specifically, it is suitably used for a method for producing an unsaturated (poly) alkylene glycol ether monomer that can be suitably used as a raw material for various polymers, and cement compositions such as cement paste, mortar, and concrete. The present invention relates to a method for producing a polymer having a (poly) alkylene glycol chain.

The polymer having a (poly) alkylene glycol chain is used as a hydrophilic polymer for various purposes, and is particularly useful as a dispersant or the like. For example, it exhibits water reduction performance for cement compositions such as cement paste, mortar and concrete, and is widely used as a cement admixture or concrete admixture, etc., and constructs civil engineering and building structures etc. from cement composition It is indispensable to do. Such a cement admixture has the effect of improving the strength, durability, and the like of the cured product by increasing the fluidity of the cement composition and reducing the water content of the cement composition. Among these water reducing agents, polycarboxylic acid cement admixtures or concrete admixtures containing polycarboxylic acid polymers exhibit high water reducing performance compared to conventional water reducing agents such as naphthalene, so high performance AE Has many achievements as a water reducing agent.

As a polycarboxylic acid polymer suitable for such a cement admixture, a copolymer of an alkenyl ether alkylene oxide adduct and an unsaturated carboxylic acid has been studied. Specifically, a binary copolymer having poly (ethylene / propylene) glycol alkenyl ether and unsaturated carboxylic acid as essential constituent units (for example, see Patent Documents 1 and 2), (1) polyethylene glycol (meta) A quaternary copolymer of allyl ether, (2) polyalkylene glycol (meth) allyl ether, (3) (meth) acrylic acid, and (4) sulfonic acid group-containing monomer (see, for example, Patent Document 3). ), (1) polyethylene glycol (meth) allyl ether, (2) polypropylene glycol (meth) allyl ether, and (3) unsaturated carboxylic acid (see, for example, Patent Document 4). It is disclosed.

Also, a copolymer of an alkylene oxide (AO) adduct of an alkenyl ether having 2 to 4 carbon atoms and methacrylic acid (for example, see Patent Document 5), a copolymer of a methallyl ether AO adduct and acrylic acid (for example, , Patent Document 6), (1) C2-C4 alkenyl ether AO adduct (addition mole number n = 1-100), and (2) C2-C4 alkenyl ether AO adduct (addition). Mole number n = 11 to 300) and (3) a terpolymer of an unsaturated monocarboxylic acid, a copolymer of (1) and (3), and a copolymer of (2) and (3). Blend (for example, refer patent document 7), C2-C4 alkenyl ether AO adduct and maleic acid copolymer (A), unsaturated polyalkylene glycol ether monomer, and no alkenyl group Non-polymerizable polyalkyl And glycol, copolymer (A) and the cement admixture comprising four components of different polymers (e.g., see Patent Document 8.) Is disclosed.
However, when used for a cement composition or the like, it has been required to have various performances and be versatile at a low cost. In addition, by improving dispersibility and water reduction, improving the fluidity retention of concrete, etc. at the production site, and making the state of concrete, etc. easier to work with, civil engineering, building structures, etc. There was room for improvement to further improve work efficiency, etc. at the construction site, and improve properties such as concrete.
JP-A-10-194808 JP-A-11-106247 JP 2000-034151 A JP 2001-220194 A JP 2002-348161 A JP 2002-121055 A JP 2003-221266 A JP-T-2006-522734

The present invention has been made in view of the above situation, and can be suitably used for various applications such as a cement admixture, and can exhibit high dispersion performance with respect to a cement composition (poly) alkylene glycol. It aims at providing the manufacturing method of the polymer which has a chain | strand.

The present inventor has made various studies on the production methods of unsaturated (poly) alkylene glycol ether monomers, and found that the unsaturated component obtained by adding a specific amount of a specific component and adding an alkylene oxide to an unsaturated alcohol. It has been found that a polymer obtained by polymerizing a (poly) alkylene glycol ether monomer and an unsaturated carboxylic acid has the advantage of improving various properties of the cement composition. It has been found that the unsaturated (poly) alkylene glycol ether monomer obtained can easily set the alkylene glycol chain length and can have a chain length according to the application. In addition, various investigations have been made on the method for producing a polymer having a (poly) alkylene glycol chain, and the presence of a specific amount of a specific component results in excellent dispersibility of the cement composition and excellent fluidity retention performance. The inventors have found that a polymer exhibiting characteristics can be obtained, and have come up with the idea that the above problems can be solved brilliantly.

That is, the present invention is a method for producing an unsaturated (poly) alkylene glycol ether monomer by addition reaction of an alkylene oxide with an unsaturated alcohol, wherein the production method is based on 100 parts by mass of the unsaturated alcohol. , A method for producing an unsaturated (poly) alkylene glycol ether monomer comprising a step of addition reaction under the condition that 0.001 to 25 parts by mass of an unsaturated (poly) alkylene glycol diether monomer is present.
The present invention is also a method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing an unsaturated (poly) alkylene glycol ether monomer, wherein the production method comprises: It includes a step of polymerizing under the condition that the unsaturated (poly) alkylene glycol diether monomer contains 0.001 to 20 parts by mass with respect to 100 parts by mass of the unsaturated (poly) alkylene glycol ether monomer ( It is also a method for producing a polymer having a poly) alkylene glycol chain.
The present invention is described in detail below.

The present invention is a method for producing an unsaturated (poly) alkylene glycol ether monomer by addition reaction of an alkylene oxide with an unsaturated alcohol. In such a production method, an addition reaction is performed under the condition that 0.001 to 25 parts by mass of an unsaturated (poly) alkylene glycol diether monomer is present with respect to 100 parts by mass of the unsaturated alcohol. Become. The content of the unsaturated (poly) alkylene glycol diether monomer is preferably 0 with respect to 100 parts by mass of the unsaturated alcohol containing an unsaturated (poly) alkylene glycol diether monomer as the unsaturated alcohol. 0.01 to 25 parts by mass, more preferably 0.05 to 20 parts by mass, still more preferably 0.1 to 15 parts by mass, and particularly preferably 0.2 to 10 parts by mass. . More preferably, it is 0.3-5 mass parts, Most preferably, it is 0.5-3 mass parts. The form containing the unsaturated (poly) alkylene glycol diether monomer may be a raw material form containing an unsaturated alcohol and an unsaturated (poly) alkylene glycol diether monomer. And it is preferable that it is a form which contains 0.001-25 mass parts of unsaturated (poly) alkylene glycol type | system | group diether monomers with respect to 100 mass parts of unsaturated alcohol in this raw material (more preferably, 0.00. 01 to 25 parts by mass). As such a raw material, the unsaturated alcohol composition mentioned later is suitable. Further, in this case, it can be achieved by adopting a method for producing an unsaturated alcohol, which will be described later, as a by-product of an unsaturated (poly) alkylene glycol diether monomer when obtaining the unsaturated alcohol, It is useful as a manufacturing process. As described above, it is preferable that the unsaturated (poly) alkylene glycol diether monomer is present in the raw material, but the unsaturated (poly) alkylene glycol is added to the raw material or reaction system. A diether monomer may be contained in the reaction system. In addition, the said unsaturated (poly) alkylene glycol type | system | group diether monomer should just contain 0.001-25 mass parts with respect to 100 mass parts of unsaturated alcohol at least once during addition reaction.

The unsaturated alcohol is a main component of the raw material in the addition reaction step, and the main component of the raw material is preferably contained in 50% by mass or more in 100% by mass of the raw material. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. Particularly preferably, all unsaturated alcohols other than unsaturated (poly) alkylene glycol diether monomers are unsaturated alcohols.
As a component other than the unsaturated alcohol and the unsaturated (poly) alkylene glycol diether monomer contained in the raw material, (poly) alkylene glycol and the like are preferable.

The unsaturated alcohol is not particularly limited as long as it has a group having an unsaturated bond and a hydroxyl group, but preferably has a group having a double bond and a hydroxyl group, and preferably has a group having a double bond and a hydroxyl group. It is more preferable to have one each. Particularly preferably, the unsaturated alcohol is represented by the following general formula (1):
X- (OR) _a -OH (1)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms. OR is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. A is a number of 0 to 300; It represents the average number of moles added of the alkylene group. X is an alkenyl group having 2 to 6 carbon atoms. The alkenyl group is more preferably an alkenyl group having 3 to 5 carbon atoms, still more preferably an alkenyl group having 3 to 4 carbon atoms, and particularly preferably an alkenyl group having 4 carbon atoms. Specific examples of the alkenyl group include 3-methyl-3-butenyl group, 4-pentenyl group, 3-pentenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 1,1-dimethyl group. C2-alkenyl group such as 2-propenyl group, methallyl group, 3-butenyl group, 2-butenyl group, carbon number 4 such as 1-methyl-2-butenyl group, carbon number such as allyl group Three alkenyl groups are preferred. Among these, a methallyl group, an allyl group, and a 3-methyl-3-butenyl group are preferable, and a methallyl group is particularly preferable.
In the above general formula, a is preferably a number from 0 to 300. More preferably, 0 to 200, 0 to 100, 0 to 50, 0 to 25, 0 to 10, 0 to 4, and more preferably in the order of a being smaller. Moreover, as alkylene oxide addition mole number, the thing of 1-50 is preferable, More preferably, it is 1-25, More preferably, it is 1-10, More preferably, it is 1-5, More preferably, it is 1-3, More preferably, 1 ˜2, more preferably 1.

Specific examples of the unsaturated alcohol include methallyl alcohol, allyl alcohol, alcohols such as 3-methyl-3-buten-1-ol, the above methallyl alcohol, allyl alcohol, and 3-methyl-3-butene-1. Among the alkylene oxide adducts of alcohols such as -ol and the above-mentioned alkylene oxide adducts, those having a relatively small alkylene oxide addition mole number a are preferred. Among them, methallyl alcohol, allyl alcohol, 3-methyl-3-buten-1-ol, methallyl alcohol-1EO (one mole of ethylene oxide added to methallyl alcohol), allyl alcohol-1EO (allyl alcohol to ethylene) 1 mole of oxide added), 3-methyl-3-buten-1-ol-1EO (1 mole of ethylene oxide added to 3-methyl-3-buten-1-ol), methallyl alcohol-2EO (2 moles of ethylene oxide added to methallyl alcohol), allyl alcohol-2EO (2 moles of ethylene oxide added to allyl alcohol), 3-methyl-3-buten-1-ol-2EO (3-methyl 2 mol of ethylene oxide added to -3-buten-1-ol Ones) is more preferable.

As described above, in the method for producing an unsaturated polyalkylene glycol ether monomer (IM), an unsaturated (poly) alkylene glycol represented by the following general formula (1) and an unsaturated (poly) alkylene glycol: Unsaturated polyalkylene glycol ether monomer which adds alkylene oxide to an unsaturated alcohol composition containing 0.001 to 25 (preferably 0.01 to 25) wt% of diether monomer (II-M) A method for producing a body is also one of the preferred embodiments of the present invention.
X- (OR) _a -OH (1)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms. OR is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. A is a number of 0 to 300; Represents the average number of moles of alkylene group added.)

The unsaturated (poly) alkylene glycol diether monomer has a group having an unsaturated bond, an alkylene glycol moiety, and a diether bond. As such an unsaturated (poly) alkylene glycol diether monomer, a form in which an unsaturated bond group and an alkylene glycol moiety are bonded by an ether bond is preferable. More preferably, the group having two unsaturated bonds is bonded to the alkylene glycol moiety with an ether bond. Particularly preferably, the unsaturated (poly) alkylene glycol diether monomer is represented by the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; It is the average number of added moles of the oxyalkylene group and is a number from 1 to 300.)
X and Y are the same or different and are preferably the same as X described above.

R ¹ O is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 4 carbon atoms. Specifically, one or more of an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxystyrene group, and the like are preferable, and among them, an oxyethylene group is preferable. When two or more oxyalkylene groups are present, the oxyethylene group is preferably 80 mol% or more. Thereby, the effect of reducing the cement particle dispersibility excellent in the polycarboxylic acid-type copolymer which has a (poly) alkylene glycol chain | strand, the viscosity of concrete, etc. can be given. When it is less than 80 mol%, for example, when the obtained polymer having a (poly) alkylene glycol chain (for example, polycarboxylic acid copolymer) is used as a cement admixture, there is a possibility that sufficient dispersibility may not be exhibited. is there. The proportion of the oxyethylene group when two or more oxyalkylene groups are present is more preferably 85 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more. Yes, and most preferably 100 mol%. As a combination in the case of having two or more kinds of oxyalkylene groups, (oxyethylene group, oxypropylene group), (oxyethylene group, oxybutylene group), (oxyethylene group, oxystyrene group) are preferable. Among these, (oxyethylene group, oxypropylene group) is more preferable. When the two or more kinds of oxyalkylene groups are present, they may be present in any form such as block, random or alternating.

The average added mole number m of the alkylene oxide to be added is suitably 1 to 300. The average added mole number is preferably in the range of specific values in the following order. That is, 1-200, 1-100, 1-50, 1-25, 1-10, 1-5, 1-3, 1-2 are preferable. If the average number of added moles exceeds 300, the copolymerizability may decrease and the dispersibility may decrease. When m is 2 or more, R ¹ O may be the same or different.

Specific examples of the unsaturated (poly) alkylene glycol diether monomer include (poly) alkylene glycol dimethallyl ether, (poly) alkylene glycol diallyl ether, and (poly) alkylene glycol di-3-methyl-3-butyl. Tenyl ether is preferred. More preferred are (poly) ethylene glycol dimethallyl ether, (poly) ethylene glycol diallyl ether, and (poly) ethylene glycol di-3-methyl-3-butenyl ether, and still more preferred are diethylene glycol dimethallyl ether and diethylene glycol diallyl ether. Diethylene glycol di-3-methyl-3-butenyl ether, ethylene glycol dimethallyl ether, ethylene glycol diallyl ether, ethylene glycol di-3-methyl-3-butenyl ether.

The production method of the unsaturated alcohol and unsaturated (poly) alkylene glycol diether monomer is not particularly limited, and various methods can be suitably used. When the unsaturated alcohol is an unsaturated (poly) oxyalkylene glycol ether, the step of reacting a halide having an unsaturated bond with (poly) oxyalkylene glycol to produce an unsaturated alcohol (step 1) It is preferred to obtain a saturated alcohol. In this case, the unsaturated (poly) alkylene glycol diether monomer can be obtained together with the unsaturated alcohol as a by-product.
The reaction temperature in Step 1 is slightly different depending on the unsaturated group-containing halide and alkylene glycol used in the reaction, and is not particularly limited, but is preferably 40 ° C to 150 ° C, more preferably 50 ° C to 100 ° C. ° C, more preferably 55 ° C to 75 ° C. The pressure during the reaction may be any of reduced pressure, normal pressure, and increased pressure, but a reaction at normal pressure is sufficient. The amount of the alkali compound used in the reaction is preferably 0.5 equivalents to 2.0 equivalents, more preferably 0.9 equivalents to 1.5 equivalents, and even more preferably 1. 0 to 1.2 equivalents. The amount of alkylene glycol used in the reaction is preferably 1.5 equivalents to 10 equivalents, more preferably 3 equivalents to 7 equivalents, and even more preferably 4 equivalents to 6 equivalents, relative to the unsaturated group-containing halide. is there. If the amount of alkylene glycol is too small, the amount of diether produced will increase, and if too large, productivity will be reduced. As a method of supplying the raw material to the reactor, it may be charged all at once in the initial stage or sequentially. An example is a method in which an alkylene glycol and an alkali compound are first reacted to form an intermediate, and then an unsaturated group-containing halide is fed and reacted. For step 1, it is necessary to use an alkali compound as the halogen scavenger, and as an example, the reaction requires a base as the halogen scavenger, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, water Examples thereof include alkaline earth metal hydroxides such as calcium oxide, alkali metal carbonates such as sodium carbonate and sodium hydrogen carbonate, and alkaline earth metal carbonates. The alkali compound may be charged into the reactor as it is, or may be charged into the reactor using water or another dispersing agent.

In step 1, the halide having an unsaturated bond is preferably a halide having an alkenyl group having 2 to 6 carbon atoms. Such an alkenyl group is preferably the same as described for X above. Although it does not specifically limit as a halogen atom couple | bonded with an alkenyl group, A chlorine atom and a bromine atom are preferable. Among these, a chlorine atom is more preferable for preventing coloration of the product and suppressing a decrease in polymerizability in the polymerization step.
As specific examples of the halide having an unsaturated bond, one or more of methallyl chloride, 3-methyl 3-butenyl chloride, allyl chloride, 3-butenyl chloride, 4-pentenyl chloride and the like are preferable. is there. More preferred are methallyl chloride and 3-methyl-3-butenyl chloride, and more preferred is methallyl chloride.

In the above step 1, the (poly) alkylene glycol is preferably one in which an alkylene oxide is repeated 1 to 4 times. When the alkylene oxide chain of the (poly) alkylene glycol is long (the alkylene oxide is repeated 5 or more times), the boiling point of the unsaturated alcohol produced in Step 1 is high. In this case, since it has a high boiling point, it is difficult to industrially purify it by distillation under reduced pressure or the like, and there is a possibility that an unsaturated alcohol with high purity cannot be obtained. More preferably (poly) oxyalkylene glycol is an alkylene oxide repeated 1-2 times.

The (poly) alkylene glycol can be represented by the general formula HO— (AO) _n2 —H. In the above formula, AO represents an oxyalkylene group having 2 to 18 carbon atoms. When n2 is 2 or more, AO may be the same or different, and n2 is the average number of added moles of the oxyalkylene group. It is. Specific examples of (poly) alkylene glycol include glycols such as ethylene glycol, propylene glycol, isobutylene glycol, butylene glycol and styrene glycol, and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyisobutylene glycol, butylene glycol and polystyrene glycol. Different alkylene glycols such as (poly) ethylene glycol (poly) propylene glycol, (poly) ethylene glycol (poly) butylene glycol, (poly) ethylene glycol (poly) styrene glycol, (poly) propylene glycol (poly) butylene glycol Copolymers are preferred.

Among the above (poly) alkylene glycols, preferably, glycols such as ethylene glycol, propylene glycol, isobutylene glycol, butylene glycol and styrene glycol, addition of alkylene glycol such as polyethylene glycol, polypropylene glycol, polyisobutylene glycol, butylene glycol and polystyrene glycol 4 or less polyalkylene glycols, (poly) ethylene glycol (poly) propylene glycol, (poly) ethylene glycol (poly) butylene glycol, (poly) ethylene glycol (poly) styrene glycol, (poly) propylene glycol (poly ) Alkylene glycol addition moles such as butylene glycol are different alkylene glycol copolymers of 4 or less

More preferably, glycols such as ethylene glycol, propylene glycol, isobutylene glycol, butylene glycol and styrene glycol, dialkylene glycols such as diethylene glycol, dipropylene glycol, diisobutylene glycol, dibutylene glycol and distyrene glycol, ethylene glycol propylene Dialkylene glycol copolymers of different alkylene glycols such as glycol, ethylene glycol butylene glycol, ethylene glycol styrene glycol, propylene glycol butylene glycol and the like.
Most preferred are ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.

In step 1 above, a halide having an unsaturated bond may be reacted with (poly) alkylene glycol, and any of the above-mentioned compounds can be suitably used, but a preferred combination (having an unsaturated bond) (Malyl chloride, ethylene glycol), (methallyl chloride, diethylene glycol), (methallyl chloride, propylene glycol), (methallyl chloride, dipropylene glycol), (meth) Ryl chloride, ethylene glycol propylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol), (3-methyl-3-butenyl chloride, diethylene glycol), (3-methyl-3-butenyl chloride, propylene) Glycol), (3-methyl-3-butenyl chloride, dipropylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol propylene glycol), (allyl chloride, ethylene glycol), (acrylic chloride, diethylene glycol) , (Allyl chloride, propylene glycol), (allyl chloride, dipropylene glycol), (allyl chloride, ethylene glycol propylene glycol) and the like. Among them, (methallyl chloride, ethylene glycol), (methallyl chloride, diethylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol), (3-methyl-3-butenyl chloride, diethylene glycol), (allyl) Chloride, ethylene glycol) and (allyl chloride, diethylene glycol) are preferred.
Thus, a production method including a step of producing an unsaturated alcohol by reacting a halide having an unsaturated bond with (poly) oxyalkylene glycol is also a preferred embodiment of the present invention.

When the unsaturated alcohol obtained in the above step 1 is used for producing an unsaturated (poly) alkylene glycol ether monomer, the unsaturated alcohol obtained by purifying the product obtained in the step 1 is used. Preferably there is. Thus, the purity of the unsaturated alcohol can be increased by purifying the product obtained in Step 1, and the yield is obtained when producing an unsaturated (poly) alkylene glycol ether monomer. Can be improved. This purification step is preferably performed after step 1 and before the production of the unsaturated (poly) alkylene glycol ether monomer, and the purified product obtained as a result is unsaturated (poly) alkylene glycol ether. It is preferable to use it for manufacture of a monomer. That is, the manufacturing method including the step of purifying the product obtained in step 1 is also one of the preferred embodiments of the present invention.

In the purification step, the product obtained in Step 1 is not particularly limited, but it is preferably purified by a method such as distillation, crystallization, extraction, or a combination thereof. Further, as a method for removing moisture contained in the product, a dehydrating agent or an adsorbent may be used, and examples thereof include magnesium sulfate and molecular sieves.

In the purification step, the purified product preferably has a water content of 2% by mass or less. That is, by performing a purification step between the above step 1 and an alkylene oxide addition reaction step (step 2) described later, the water content of the unsaturated alcohol obtained in step 1 is set to 2% by mass or less, and after the purification, In 100% by mass of the product, the water content is preferably 2% by mass or less. More preferably, it is 1.5 mass% or less, More preferably, it is 0.5 mass% or less, Especially preferably, it is 0.25 mass% or less, Most preferably, it is 0.1 mass% or less. A high water content is not preferable because the amount of (poly) alkylene glycol as a by-product increases when the alkylene oxide addition reaction is performed in Step 2.

As described above, the purification step is not particularly limited as long as it can be purified by various methods and the water content of the purified product is 2% by mass or less. A method of distilling the product is preferred. By distilling the product obtained in step 1, it is industrially advantageous compared to other methods, the purity of the unsaturated alcohol can be easily increased, and when the unsaturated alcohol is used as a raw material, It can be manufactured with good yield in the subsequent steps. Thus, in the purification step, a method for producing a polycarboxylic acid copolymer in which the product obtained in Step 1 is distilled is also one of the preferred embodiments of the present invention.

In the distillation step, the distillation operation may be performed in one step, or may be performed in two or more steps, such as a rough distillation step and a rectification step for removing water in the system. Alternatively, a method may be used in which a crude distillation for removing water is performed at the stage where alkylene glycol and an alkali compound are first reacted, and then an unsaturated group-containing halide is reacted to carry out distillation purification. In the crude distillation process for removing water, it is preferable to use an apparatus with an oil / water separation tank. Can be reduced. In this step, a single distillation or a number of distillation stages may be provided. In order to remove water more efficiently, for example, an azeotropic agent such as cyclohexane or toluene may be used. As the distillation apparatus, it is preferable to use a packed column or a plate column and perform distillation while applying reflux. As the temperature at the time of distillation, the temperature of the bottom of the packed column or the plate column is preferably 180 ° C. or lower, more preferably 150 ° C. or lower. This is because if the temperature is too high, polymerization of the unsaturated group portion or decomposition of the target compound may occur. The optimum operating pressure during distillation varies depending on the unsaturated alcohol to be produced, but may be set so as to be within the above temperature range.
The whole or part of the (poly) alkylene glycol recovered in the purification step may be reused as a raw material.
Further, the method for separating and removing the halide of the alkali compound produced in step 1, such as sodium chloride and calcium chloride, is not particularly limited, but for example, a device such as a pressure filter or a centrifuge Can be used for solid-liquid separation. The separation and removal of the halide of the alkali compound may be performed immediately after the reaction in the step 1, or may be performed after or during the purification step.

The unsaturated (poly) alkylene glycol ether monomer is obtained by addition reaction of an alkylene oxide to an unsaturated alcohol, and the above-mentioned unsaturated alcohol is preferable. The alkylene oxide to be added to the unsaturated alcohol is preferably an alkylene oxide having 2 to 18 carbon atoms. More preferably, it is a C2-C8 alkylene oxide, More preferably, it is a C2-C4 alkylene oxide. Specifically, one or more of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like are preferable, and ethylene oxide is particularly preferable. When adding 2 or more types of alkylene oxide, it is preferable that ethylene oxide is 80 mol% or more. This maintains a balance between hydrophilicity and hydrophobicity and is excellent in polycarboxylic acid-based copolymers having a (poly) alkylene glycol chain obtained by polymerizing unsaturated (poly) alkylene glycol ether monomers. It is possible to give the effect of reducing the cement particle dispersibility and the viscosity of concrete. If it is less than 80 mol%, the hydrophobicity of the unsaturated (poly) alkylene glycol ether monomer becomes stronger and the hydrophobicity of the resulting polymer also becomes stronger. It causes cause. More preferably, it is 85 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 100 mol%.
As a combination in the case of adding two or more kinds of alkylene oxides, (ethylene oxide, propylene oxide), (ethylene oxide, butylene oxide), and (ethylene oxide, styrene oxide) are preferable. Among these, (ethylene oxide, propylene oxide) is more preferable.
When the two or more kinds of alkylene oxides are added, each addition method may be any addition form such as block addition, random addition, and alternating addition. Further, the step of adding an alkylene oxide to an unsaturated alcohol to produce an unsaturated polyalkylene glycol ether monomer having a polyalkylene oxide chain is referred to as step 2. In step 2, the unsaturated alcohol is preferably an unsaturated (poly) alkylene glycol ether monomer. The unsaturated alcohol used in the above step 2 is produced in the step 1. More preferably, it is an unsaturated alcohol obtained by purifying the product obtained in Step 1. Thus, by purifying the product obtained in step 1, the purity of the unsaturated alcohol can be increased, and the yield in step 2 and step 3 described later can be improved. This purification step is performed between steps 1 and 2, and is a production method for purifying the unsaturated alcohol after step 1 and before step 2, and the purified product obtained as a result is preferably used for step 2. It is. In Step 2, when an addition reaction is performed with an unsaturated (poly) alkylene glycol ether monomer which is a preferred form of the unsaturated alcohol, the unsaturated (poly) alkylene glycol ether ether before the addition reaction is carried out It is possible to obtain an unsaturated (poly) alkylene glycol ether monomer having an alkylene oxide addition number larger than that of the product.

In the addition reaction, the addition temperature is preferably in the range of 80 to 170 ° C. More preferably, it is 90-160 degreeC, More preferably, it is 100-150 degreeC. When the addition reaction temperature is too high, side reaction products tend to increase. For example, when a polymer for a cement dispersant is obtained using the obtained reaction product, performance such as water reduction performance tends to decrease. On the other hand, if it is too low, the addition speed becomes slow and the productivity decreases, which is not preferable. In step 2, the reaction time is preferably within 50 hours. More preferably, it is within 40 hours, More preferably, it is within 30 hours. If the reaction time is too long, the amount of by-products tends to increase. The addition reaction is preferably performed under pressure. The pressure at the start of the addition reaction is preferably 0.01 to 0.5 MPa. More preferably, it is 0.05-0.3 MPa, More preferably, it is 0.1-0.2 MPa. The pressure during the addition reaction is preferably 0.9 MPa or less.

In the addition reaction, it is preferable to use a catalyst. Catalysts include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium hydroxide, metal hydrides such as sodium hydride and potassium hydride, and organic materials such as butyl lithium, methyl lithium and phenyl lithium. Metallic compounds, Lewis acids such as boron trifluoride and titanium tetrachloride, and metal alkoxides such as sodium methoxide and potassium methoxide are preferred. More preferred are sodium hydroxide, potassium hydroxide, sodium hydride and boron trifluoride, and still more preferred are sodium hydroxide and potassium hydroxide. As the catalyst concentration, it is preferable that the weight ratio of the catalyst to the theoretical amount of alkylene oxide adduct calculated from the charged raw material is 10,000 ppm or less. More preferably, it is 8000 ppm or less, More preferably, it is 5000 ppm or less, Most preferably, it is 3000 ppm or less. If the catalyst concentration is too high, a large amount of by-products tend to be generated.
In the above step 2, the addition reaction can be carried out either batchwise or continuously, and can be appropriately selected depending on the reaction conditions and the like.

The unsaturated (poly) alkylene glycol ether monomer has a group having an unsaturated bond, an alkylene glycol moiety, and an ether bond. Such an unsaturated (poly) alkylene glycol ether monomer is obtained by addition reaction of the above-mentioned alkylene oxide to the above-mentioned unsaturated alcohol. Specifically, the unsaturated (poly) alkylene glycol ether monomer is represented by the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents an average addition mole number of an oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (3), X is preferably the same as described above.
R ² O is an alkylene oxide moiety added to an unsaturated alcohol. That is, R ² O is an oxyalkylene group having 2 to 18 carbon atoms, and the alkylene oxide described for the alkylene oxide is added as an oxyalkylene group. This is as described for the alkylene oxide.

The average added mole number n of the alkylene oxide to be added is suitably 1 to 300. The average added mole number is preferably larger to some extent, and is preferably a specific value or more in the following order (a larger numerical value is preferable). That is, 10 or more, 25 or more, 35 or more, 50 or more, 75 or more, 100 or more, 110 or more, 120 or more, 135 or more, 150 or more, 160 or more, 170 or more, 180 or more are preferable. Moreover, it is also preferable that the average added mole number is not too large, and it is preferable that the average added mole number is not more than a specific value in the following order (a smaller numerical value is preferable). That is, 280 or less, 250 or less, 225 or less, and 200 or less are preferable. Furthermore, the range of the average added mole number n of alkylene oxide is preferably in the range of 110 to 180. More preferably, it is 110-170, More preferably, it is 120-160, Most preferably, it is the range of 130-150. The smaller the average number of added moles, the lower the hydrophilicity and the lower the effect of repelling the cement particles, which may reduce the dispersion performance of the resulting copolymer. When a (poly) alkylene glycol ether monomer is used for copolymerization, the copolymerization reactivity may be reduced.

R ³ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, or an alkynyl group. More preferably, they are a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, and an alkynyl group, and more preferably a hydrogen atom and a linear chain having 1 to 4 carbon atoms. Or, it is a branched alkyl group, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, or an alkynyl group, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the (poly) alkylene glycol ether monomers include (poly) alkylene glycol methallyl ethers, (poly) alkylene glycol allyl ethers, and (poly) alkylene glycol 3-methyl-3-butenyl ethers. Etc. are suitable.
Specifically, polyethylene glycol methallyl ethers, polyethylene glycol allyl ethers, and polyethylene glycol 3-methyl-3-butenyl ethers are preferable. More preferred are polyethylene glycol methallyl ethers.

As described above, the unsaturated (poly) alkylene glycol diether monomer has the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; The average number of moles added of the oxyalkylene group and a number of 1 to 300.)
The unsaturated (poly) alkylene glycol ether monomer is represented by the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents an average addition mole number of an oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) A method for producing an unsaturated (poly) alkylene glycol ether monomer represented by: Is also one of the preferred embodiments of the present invention.

The present invention also provides an unsaturated alcohol composition comprising an unsaturated alcohol and an unsaturated (poly) alkylene glycol diether monomer, wherein the unsaturated alcohol is represented by the following general formula (4):
X- (OR) _b -OH (4)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms; OR is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; b is a number of 1 to 300; The unsaturated (poly) alkylene glycol diether monomer is represented by the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; The average added mole number of the oxyalkylene group, which is a number of 1 to 300. It is also an unsaturated alcohol composition containing 0.001 to 25 parts by mass of an alkylene glycol diether monomer.

As said unsaturated alcohol composition, 0.001-25 mass parts of unsaturated (poly) alkylene glycol diether monomers will exist with respect to 100 mass parts of unsaturated alcohol. Such an unsaturated alcohol composition can be suitably used as a raw material in the production of the above-mentioned unsaturated (poly) alkylene glycol ether monomer, for example. As content of an unsaturated (poly) alkylene glycol type | system | group diether monomer, when b in the said General formula (4) is 1-10, Preferably it is 0.05-100 with respect to 100 mass parts of unsaturated alcohol. 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.2 to 10 parts by mass, particularly preferably 0.3 to 5 parts by mass, and most preferably. Is 0.5-3 parts by mass. When b in the said General formula (4) exceeds 10, Preferably it is 0.0025-15 mass parts with respect to 100 mass parts of unsaturated alcohol, More preferably, it is 0.005-10 mass parts. More preferably, the amount is 0.01 to 5 parts by mass, and particularly preferably 0.015 to 3 parts by mass.

The unsaturated alcohol contained in the unsaturated alcohol composition is represented by the general formula (4). In the said General formula (4), b is a number of 1-300, and represents the average addition mole number of an oxyalkylene group. As b, 1-300 is preferable. More preferably, 1 to 200, 1 to 100, 1 to 50, 1 to 25, 1 to 10, 1 to 4, 1 to 3, 1 to 2, 1, and b are more preferable in ascending order.
In the general formula (4), X and OR are preferably the same as described above. The unsaturated (poly) alkylene glycol diether monomer is preferably as described above. That is, X, Y, R ¹ O, m in the general formula (2) and specific examples of the unsaturated (poly) alkylene glycol diether monomer are preferably the same as described above.

The unsaturated alcohol composition may be obtained by mixing an unsaturated alcohol and an unsaturated (poly) alkylene glycol diether monomer, but when the unsaturated alcohol described above is obtained, the unsaturated (poly) alkylene is obtained. It is preferably obtained by a method for producing an unsaturated alcohol which produces a glycol diether monomer as a by-product. That is, the unsaturated alcohol composition obtained by reacting a halide having an unsaturated bond with (poly) alkylene glycol is also a preferred embodiment of the present invention. It is.
In the reaction of reacting the halide having an unsaturated bond with (poly) alkylene glycol, the halide having an unsaturated bond, (poly) alkylene glycol, reaction conditions, and the like may be the same as described above. preferable. In this case, the said process 1 will obtain the composition containing an unsaturated alcohol and an unsaturated (poly) alkylene glycol type | system | group diether monomer, and if necessary, a distillation process, unsaturated alcohol, and unsaturated ( Other steps such as a step of adjusting the ratio with the poly) alkylene glycol diether monomer may be used.
The other components contained in the unsaturated alcohol composition are not particularly limited as long as they do not hinder the stability of the unsaturated alcohol composition. For example, when the unsaturated alcohol composition is obtained by a reaction of reacting the halide having an unsaturated bond with (poly) alkylene glycol, various by-products remaining after the reaction are included. .

The present invention is also a method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing an unsaturated (poly) alkylene glycol ether monomer, the production method comprising: It includes a step of polymerizing under the condition that the unsaturated (poly) alkylene glycol diether monomer contains 0.001 to 20 parts by mass with respect to 100 parts by mass of the unsaturated (poly) alkylene glycol ether monomer ( It is also a method for producing a polymer having a poly) alkylene glycol chain. In the present invention, by containing an unsaturated (poly) alkylene glycol-based diether monomer, the resulting polymer having a (poly) alkylene glycol chain has excellent cement composition dispersion performance, fluidity retention performance, and the like. It can exhibit the characteristics and can be suitably used for various applications such as a cement admixture, an inorganic pigment dispersant, and a builder for detergent.

In the said manufacturing method, on condition that 0.001-20 mass parts of unsaturated (poly) alkylene glycol type | system | group diether monomers exist with respect to 100 mass parts of unsaturated (poly) alkylene glycol type ether monomers. Then, an addition reaction is performed. If it is less than 0.001% by mass, the resulting polymer having a (poly) alkylene glycol chain may not be sufficiently excellent in cement composition dispersion performance, fluidity retention performance, etc., and 20% by mass When it exceeds, there exists a possibility that the cement composition dispersibility may fall. As content of an unsaturated (poly) alkylene glycol type | system | group diether monomer, when b in the said General formula (4) is 1-10, it is 100 mass parts of unsaturated (poly) alkylene glycol type | system | group ether monomers. On the other hand, it is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.2 to 10 parts by mass, and particularly preferably 0.3. -5 mass parts, and most preferably 0.5-3 mass parts. When b in the general formula (4) exceeds 10, it is preferably 0.0025 to 15 parts by mass, more preferably 100 parts by mass of the unsaturated (poly) alkylene glycol ether monomer. It is 0.005-10 mass parts, More preferably, it is 0.01-5 mass parts, Most preferably, it is 0.015-3 mass parts.
In addition, the said unsaturated (poly) alkylene glycol type | system | group diether monomer contains 0.01-25 mass parts with respect to 100 mass parts of unsaturated (poly) alkylene glycol type ether monomers at least once in the said manufacturing method. If that happens.

The form containing the unsaturated (poly) alkylene glycol diether monomer includes (1) an unsaturated (poly) alkylene glycol ether monomer and an unsaturated (poly) alkylene glycol diether monomer. Form using raw materials, (2) adding unsaturated (poly) alkylene glycol diether monomer to the reaction system by adding unsaturated (poly) alkylene glycol diether monomer to the raw material or reaction system A form is suitable and either one may be used and both may be used together. In addition, when using the unsaturated (poly) alkylene glycol ether monomer obtained by the above production method as a raw material, since it contains an unsaturated (poly) alkylene glycol diether monomer as a by-product, The form (1) can simplify the manufacturing process and is advantageous in terms of the manufacturing process.
As a form of said (1), it is 0.001-20 with respect to 100 mass parts of unsaturated (poly) alkylene glycol type | system | group ether monomers in a raw material with an unsaturated (poly) alkylene glycol type | system | group diether monomer. A form containing parts by mass is preferable. In this case, when obtaining an unsaturated (poly) alkylene glycol ether monomer, it is preferable to use a production method or production raw material containing an unsaturated (poly) alkylene glycol diether monomer. This can be achieved by using the unsaturated (poly) alkylene glycol ether monomer obtained by the above-mentioned production method as a raw material, and is useful as a raw material. Thus, it is a preferable embodiment that the unsaturated (poly) alkylene glycol diether monomer is present in the raw material as a by-product. That is, a method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing an unsaturated (poly) alkylene glycol ether monomer, the production method comprising unsaturated ( A (poly) alkylene glycol chain comprising a step of polymerizing using a monomer raw material containing 0.001 to 20% by mass of an unsaturated (poly) alkylene glycol diether monomer as a poly) alkylene glycol ether monomer A method for producing a polymer having the same is also one of the preferred embodiments of the present invention.

As said monomer raw material, 0.001-20 mass% of unsaturated (poly) alkylene glycol diether monomers are contained. If it is less than 0.001% by mass, the resulting polymer having a (poly) alkylene glycol chain may not be sufficiently excellent in cement composition dispersion performance, fluidity retention performance, etc., and 20% by mass When it exceeds, there exists a possibility that the cement composition dispersibility may fall. The content of the unsaturated (poly) alkylene glycol diether monomer is preferably 0.0025 to 15% by mass and more preferably 0.005 to 10% with respect to 100% by mass of the monomer raw material. It is 0.01 mass%, More preferably, it is 0.01-5 mass%, Most preferably, it is 0.015-3 mass%.

The unsaturated (poly) alkylene glycol ether monomer is not particularly limited as long as it has a group having an unsaturated bond, an alkylene glycol moiety, and an ether bond, but the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents the average number of added moles of the oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In the above formula, X, R ² O, n, and R ³ are each preferably as described above.
The unsaturated (poly) alkylene glycol ether monomer is not particularly limited as long as it has the structure described above, but is preferably obtained by a production method in which an alkylene oxide is added to the unsaturated alcohol described above. .

The unsaturated (poly) alkylene glycol diether monomer has an unsaturated bond group, an alkylene glycol moiety, and a diether bond. As such an unsaturated (poly) alkylene glycol diether monomer, a form in which an unsaturated bond group and an alkylene glycol moiety are bonded by an ether bond is preferable. More preferably, the group having two unsaturated bonds is bonded to the alkylene glycol moiety with an ether bond. Specifically, the unsaturated (poly) alkylene glycol diether monomer is represented by the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; It is an average addition mole number of an oxyalkylene group and is a number of 1 to 300). In the above formula, X, R ¹ O, m and Y are preferably the same as those described above.

The unsaturated (poly) alkylene glycol diether monomer is represented by the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; The average number of moles added of the oxyalkylene group and a number of 1 to 300.)
The unsaturated (poly) alkylene glycol ether monomer is represented by the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents an average addition mole number of an oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) A method for producing a polymer having a (poly) alkylene glycol chain represented by: This is one of the preferred embodiments of the present invention.

Further, a polymer having a polyalkylene glycol chain obtained by polymerizing a monomer component (M) containing an unsaturated polyalkylene glycol ether monomer (IM) represented by the following general formula (3): In the production method, an unsaturated (poly) alkylene glycol diether monomer (II-M) represented by the following general formula (2) is used as at least a part of the composition containing the unsaturated polyalkylene glycol ether monomer. ) In an amount of 0.001 to 20 wt% of an unsaturated polyalkylene glycol-based ether monomer, and a method for producing a polymer having a polyalkylene glycol chain using 10 wt% or more of all components is also disclosed in the present invention. One of the preferred forms.
_{^{X-O- (R 2 O)}} n -R 3 (3)
X represents an alkenyl group having 2 to 6 carbon atoms, R ² O represents an oxyalkylene group having 2 to 18 carbon atoms, and when n is 2 or more, each R ² O may be the same or different. , N is the average number of added moles of the oxyalkylene group and is a number from 1 to 300, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
X—O— (R ¹ O) _m —Y (2)
X and Y each independently represent an alkenyl group having 2 to 6 carbon atoms, R ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, and when m is 2 or more, R ¹ O is the same or different. And m is the average number of moles added of the oxyalkylene group and is a number from 1 to 300.

In the method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing the unsaturated (poly) alkylene glycol ether monomer, the monomer raw material is unsaturated (poly ) An alkylene glycol ether monomer and an unsaturated (poly) alkylene glycol diether monomer are included. The monomer component other than the above two components can be appropriately selected according to the polymer having a (poly) alkylene glycol chain to be obtained, and is not particularly limited, and is an unsaturated carboxylic acid, other components described later. Etc. are suitable.
In the method for producing the polymer having the (poly) alkylene glycol chain, the monomer to be polymerized and the ratio of the monomer are selected according to the target polymer, and the reaction conditions according to the monomer are selected. It is preferable to carry out the polymerization by appropriately setting the above. For example, a process (referred to as process 3) of polymerizing an unsaturated (poly) alkylene glycol ether monomer and an unsaturated carboxylic acid to obtain a polycarboxylic acid copolymer will be described below.

Step 3 is a process for copolymerizing an unsaturated (poly) alkylene glycol ether monomer and an unsaturated carboxylic acid.
The unsaturated (poly) alkylene glycol ether monomer (also referred to as monomer (i)) is obtained by a production method including the alkylene oxide addition step (also referred to as step 2). Are preferable, and one or more of them may be used. When using 2 or more types, the combination of 2 or more types in which the average addition mole number n of an oxyalkylene group is 1-300 may be sufficient. At this time, the difference in the average added mole number n of the oxyalkylene group is preferably 10 or more, and more preferably 20 or more. For example, a combination of those having an average added mole number n of 50 to 300 and those having an average added mole number n of 1 to 50 is suitable. In this case, the difference of n is preferably 10 or more, more preferably 20 or more. Moreover, as these ratios, it is preferable that the ratio (weight ratio) of those whose average addition mole number n is 50-300 is larger than that whose average addition mole number n is 1-50. Also in the case of using three or more different monomers (i), the difference in the average added mole number n is preferably 10 or more, and more preferably 20 or more.

Examples of the unsaturated carboxylic acid (also referred to as monomer (ii)) include acrylic acid, methacrylic acid, crotonic acid, and monovalent metal salts, divalent metal salts, quaternary ammonium salts, and organic amine salts thereof. Unsaturated monocarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, etc .; monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc. One or two or more of these can be used. Among these, acrylic acid, methacrylic acid, and maleic acid are more preferable, and acrylic acid is more preferable. That is, the unsaturated carboxylic acid preferably contains at least acrylic acid or a salt thereof. By including a structure derived from acrylic acid or a salt thereof, the resulting polycarboxylic acid copolymer can exhibit excellent dispersibility in a small amount.

In step 3, other components (also referred to as monomer (iii)) may be contained. Specifically, unsaturated (poly) alkylene glycol ether monomer (monomer (i )) And / or a monomer (copolymerizable monomer) copolymerizable with unsaturated carboxylic acid (monomer (ii)). Examples of the copolymerizable monomer include half esters and diesters of the unsaturated dicarboxylic acids and alcohols having 1 to 30 carbon atoms; and the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms. Half amides and diamides; half esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acids; Half esters and diesters of saturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of these glycols of 2 to 500; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Acrylate, glycidyl (meth) acryl Esters of unsaturated monocarboxylic acids such as carbonates, methyl crotonates, ethyl crotonates, and propyl crotonates with alcohols having 1 to 30 carbon atoms; alkylene having 1 to 30 carbon atoms and alkylene having 2 to 18 carbon atoms Esters of alkoxy (poly) alkylene glycol to which 1 to 500 moles of oxide are added and unsaturated monocarboxylic acids such as (meth) acrylic acid; (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, ( 1-500 molar adducts of alkylene oxides of 2-18 carbon atoms to unsaturated monocarboxylic acids such as (meth) acrylic acid, such as poly) butylene glycol monomethacrylate; maleamic acid and 2-18 carbon atoms Glycols or moles of these glycols added Half amides with 2 to 500 polyalkylene glycols; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene (Poly) alkylene glycol di (meth) acrylates such as glycol di (meth) acrylate; multifunctional such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate ( (Meth) acrylates; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- ( (Meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) Acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamide methylsulfonic acid, (meth) acrylamide ethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid Unsaturated sulfonic acids such as monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc .; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms A Vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene and p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1, Alkanediol mono (meth) acrylates such as 6-hexanediol mono (meth) acrylate; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; ) Unsaturated amides such as acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; Unsaturated cyanides such as (meth) acrylonitrile, α-chloroacrylonitrile; Unsaturated esters such as vinyl acetate and vinyl propionate; Unsaturated amines such as aminoethyl acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine; Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; Vinyl ethers or ants such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether, etc. Ethers: polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid) , Polydimethylsiloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis Siloxane derivatives such as-(1-propyl-3-methacrylate); and the like, and one or more of these can be used. In particular, as copolymerizable monomers, unsaturated such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate, etc. Esters of monocarboxylic acids and alcohols having 1 to 30 carbon atoms; alkoxy (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to alcohols having 1 to 30 carbon atoms and (meta ) Esters with unsaturated monocarboxylic acids such as acrylic acid; (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) butylene glycol monomethacrylate and other (meth) acrylic acid and other unsaturated mono Carbon raw materials for carboxylic acids Equimolar adducts of 1 to 500 number 2 to 18 alkylene oxide are preferred.

As the blending ratio of the above monomers (i) to (iii), unsaturated (poly) alkylene glycol ether monomer (monomer (i)), unsaturated carboxylic acid (monomer (ii)) And it is preferable that it is the following ranges with respect to a total of 100 mass% of the other component (monomer (iii)) added as needed.
The blending ratio of the monomer (i) is preferably 1% by mass or more. When the blending ratio is less than 1% by mass, when the resulting polycarboxylic acid copolymer is used as a cement admixture, the dispersibility with respect to cement tends to be reduced. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more, Most preferably, it is 30 mass% or more, Most preferably, it is 45 mass% or more.

The upper limit of the proportion of monomer (ii) is suitably 60% by mass or less in terms of sodium salt. When the amount exceeds 60% by mass, when the resulting polycarboxylic acid copolymer is used as a cement admixture, the dispersion performance deteriorates with time (slump loss), and sufficient dispersion performance may not be exhibited. Preferably, it is 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, particularly preferably 30% by mass or less, and most preferably 25% by mass or less. Moreover, it is preferable that it is below a specific value in the following order (a smaller numerical value is preferable). It is more preferable in this order that they are 20 mass% or less, 15 mass% or less, and 10 mass% or less. Moreover, as a minimum of the mixture ratio of monomer (ii), it is preferable that it is 1 mass% or more. More preferably, it is 2 mass% or more, More preferably, it is 3 mass% or more, Most preferably, it is 4 mass% or more.

The blending ratio of the monomer (iii) is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 70% by mass or less, more preferably 60% by mass or less in Step 3. More preferably, it is 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less. Moreover, it is preferable that it is below a specific value in the following order (it is preferable that a numerical value is smaller), and it is more preferable in this order that it is 20 mass% or less and 10 mass% or less.

The blending ratio of each component in the step 3 is, for example, monomer (i) / monomer (ii) / monomer (iii) = 1 to 99/1 to 60/0 to 70 (mass%). A range is preferred. More preferably, monomer (i) / monomer (ii) / monomer (iii) = 5 to 99/1 to 50/0 to 60 (mass%), and more preferably 10 to 99. / 1 to 40/0 to 50 (mass%), particularly preferably 25 to 98/2 to 35/0 to 40 (mass%), and most preferably 40 to 97/3 to 30/0. It is -30 (mass%), Most preferably, it is 45-97 / 3-25 / 0-30. (However, the sum of monomer (i), monomer (ii) and monomer (iii) is 100% by mass).

Copolymerization for obtaining the polycarboxylic acid copolymer can be carried out by a known method such as solution polymerization or bulk polymerization. The solution polymerization can be carried out either batchwise or continuously. Solvents used here include water; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; benzene, toluene, xylene, cyclohexane, n-hexane and the like. Aromatic or aliphatic hydrocarbons of the above; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; and the like. From the viewpoint of solubility, it is preferable to use at least one selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms. Among them, it is more preferable to use water as a solvent because the solvent removal step can be omitted. .

When aqueous solution polymerization is performed, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′-azobis-2 -Azoamidine compounds such as methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2'-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, and azonitrile compounds such as 2-carbamoylazoisobutyronitrile Water-soluble azo-based initiators such as sodium bisulfite are used. In this case, Fe (II) salts such as alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite, and molle salts, hydroxymethanesulfinic acid Sodium dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), erythorbine Accelerators such as acids (salts) can be used in combination. Among these, a combination of hydrogen peroxide and an accelerator such as L-ascorbic acid (salt) is preferable.

For solution polymerization using a lower alcohol, aromatic or aliphatic hydrocarbon, ester compound or ketone compound as a solvent, peroxides such as benzoyl peroxide, lauroyl peroxide, sodium peroxide; t-butyl hydroperoxide, cumene hydro Hydroperoxides such as peroxides; azo compounds such as azobisisobutyronitrile; etc. are used as radical polymerization initiators. In this case, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various radical polymerization initiators or combinations of radical polymerization initiators and accelerators.

When performing bulk polymerization, as a radical polymerization initiator, peroxides such as benzoyl peroxide, lauroyl peroxide and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azobisisobutyro An azo compound such as nitrile is used.

The reaction temperature at the time of copolymerization is not particularly limited. For example, when persulfate is used as an initiator, the reaction temperature is suitably in the range of 30 to 100 ° C, preferably in the range of 40 to 95 ° C, A range of 45 to 90 ° C is more preferable. When the initiator is a combination of hydrogen peroxide and L-ascorbic acid (salt) as an accelerator, the reaction temperature is suitably in the range of 30 to 100 ° C, preferably in the range of 40 to 95 ° C, 45 A range of ˜90 ° C. is more preferable.
The polymerization time during the copolymerization is not particularly limited, but for example, a range of 0.5 to 10 hours is appropriate, preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. If the polymerization time is too long or too short from this range, the polymerization rate and productivity are lowered, which is not preferable.
The amount of all monomer components used in the copolymerization is suitably in the range of 10 to 99% by mass, preferably in the range of 20 to 98% by mass, based on the total raw materials including other raw materials and the polymerization solvent. The range of 25-95 mass% is more preferable, the range of 30-90 mass% is further more preferable, the range of 30-80 mass% is especially preferable, and the range of 40-70 mass% is the most preferable. In particular, if the amount of all the monomer components used is too lower than this range, it is not preferable because the polymerization rate is lowered and the productivity is lowered.

The method of charging each monomer into the reaction vessel is not particularly limited, the method of initially charging the entire amount into the reaction vessel at once, the method of dividing or continuously charging the entire amount into the reaction vessel, and the initial charging into the reaction vessel. Any method may be employed in which the remainder is divided or continuously charged into the reaction vessel. Specifically, a method in which the total amount of monomer (i) and the total amount of monomer (ii) are continuously charged into the reaction vessel, a part of monomer (i) is initially charged into the reaction vessel, and A method of continuously charging the remainder of the monomer (i) and the whole amount of the monomer (ii) into the reaction vessel, or a part of the monomer (i) and a part of the monomer (ii) in the reaction vessel A method in which the remainder of monomer (i) and the remainder of monomer (ii) are alternately fed into the reaction vessel in several divided portions, and the entire amount of monomer (i) is added to the reaction vessel. First, the whole amount of monomer (ii) is continuously or dividedly charged into the reaction vessel, and the whole amount of monomer (i) and a part of monomer (ii) are initially charged into the reaction vessel. And the remaining monomer (ii) can be continuously or dividedly charged into the reaction vessel. Furthermore, by changing the charging rate of each monomer into the reaction vessel in the middle of the reaction continuously or stepwise, changing the weight ratio of each monomer per unit time continuously or stepwise, Two or more types of copolymers having different ratios of the structural unit (I) derived from the monomer (i) and the structural unit (II) derived from the monomer (ii) are synthesized simultaneously during the polymerization reaction. Also good. The radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.

In the case of copolymerization, a chain transfer agent can be used for adjusting the molecular weight of the obtained copolymer. In particular, a chain transfer agent is preferably used when the polymerization reaction is performed at a high concentration in which the amount of all monomer components used is 30% by mass or more based on the total amount of raw materials used during polymerization. Examples of chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, etc. These thiol chain transfer agents can be used, and two or more types of chain transfer agents can be used in combination. Furthermore, in order to adjust the molecular weight of the copolymer, it is also effective to use a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as the monomer (iii).

In order to obtain a copolymer having a predetermined molecular weight with good reproducibility, it is important to allow the copolymerization reaction to proceed in a stable manner. 5 ppm or less is preferable. More preferably, it is 0.01-4 ppm, More preferably, it is 0.01-2 ppm, Most preferably, the range of 0.01-1 ppm is good. In addition, what is necessary is just to make the dissolved oxygen concentration of the type | system | group containing a monomer into the said range, when nitrogen substitution etc. are performed after adding a monomer to a solvent.
The dissolved oxygen concentration of the solvent may be adjusted in a polymerization reaction tank, or a solvent whose dissolved oxygen amount is adjusted in advance may be used. Examples of the method for driving off oxygen in the solvent include the following methods (1) to (5).

(1) After an inert gas such as nitrogen is pressure-filled in a sealed container containing a solvent, the partial pressure of oxygen in the solvent is lowered by lowering the pressure in the sealed container. You may reduce the pressure in an airtight container under nitrogen stream.
(2) The liquid phase portion is vigorously stirred for a long time while the gas phase portion in the container containing the solvent is replaced with an inert gas such as nitrogen.
(3) An inert gas such as nitrogen is bubbled in the solvent in the container for a long time.
(4) The solvent is once boiled and then cooled in an inert gas atmosphere such as nitrogen.
(5) A static mixer (static mixer) is installed in the middle of the pipe, and an inert gas such as nitrogen is mixed in the pipe for transferring the solvent to the polymerization reaction tank.

In the above copolymerization reaction, when a solvent is used, the polymerization may be performed at a pH of 5 or more. In that case, the polymerization rate is lowered, and at the same time, the copolymerizability is deteriorated and the performance as a cement admixture is lowered. It is preferable to carry out the copolymerization reaction at a pH of less than 5. The pH can be adjusted by, for example, inorganic salts such as monovalent metal or divalent metal hydroxides and carbonates; alkaline substances such as ammonia; organic amines; inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, acetic acid It can be carried out using organic acids such as p-toluenesulfonic acid.

The present invention includes (1) a method for producing an unsaturated (poly) alkylene glycol ether monomer by addition reaction of an alkylene oxide with an unsaturated alcohol, and (2) an unsaturated (poly) alkylene glycol ether ether unit. This is a method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing a monomer, and in particular, an unsaturated (poly) alkylene glycol ether monomer through three steps It is preferable to produce a polycarboxylic acid copolymer by copolymerizing a monomer component essentially containing an unsaturated carboxylic acid. As the above three steps, step 1: a step of reacting a halide having an unsaturated bond with (poly) alkylene glycol to obtain an unsaturated alcohol, step 2: an alkylene oxide being added to the unsaturated alcohol obtained in step 1 A step of obtaining an unsaturated (poly) alkylene glycol ether monomer by addition, and a step 3: polymerizing the unsaturated (poly) alkylene glycol ether monomer obtained in step 2 and an unsaturated carboxylic acid. In this step, a polycarboxylic acid polymer obtained is obtained.

That is, a method for producing a polycarboxylic acid copolymer by copolymerizing a monomer component essentially comprising an unsaturated (poly) alkylene glycol ether monomer and an unsaturated carboxylic acid, the production The method includes the step 1 of reacting a halide having an unsaturated bond with a (poly) alkylene glycol to produce an unsaturated alcohol, and adding an alkylene oxide to the unsaturated alcohol to produce an unsaturated (poly) alkylene glycol ether. A method for producing a polycarboxylic acid copolymer comprising a step 2 for producing a monomer and a step 3 for copolymerizing an unsaturated (poly) alkylene glycol ether monomer and an unsaturated carboxylic acid, This is one of the preferred embodiments of the present invention.

By including the above three steps, an inexpensive halide having an unsaturated bond can be used as a raw material, the raw material cost can be sufficiently reduced, and the cost for producing a polycarboxylic acid copolymer can be reduced. You can go down. Moreover, the alkylene chain length of the unsaturated (poly) alkylene glycol ether monomer can be set to a suitable length according to the application. Furthermore, the polycarboxylic acid copolymer obtained by the above production method can exhibit an effect of being superior in the effect of dispersing cement particles than a polycarboxylic acid polymer produced using a conventional unsaturated alcohol as a starting material. Therefore, it can be suitably used for various applications. In the specification, “unsaturated polyoxyalkylene” or “having a (poly) alkylene oxide chain” includes a case where only one alkylene oxide is attached. That is, the polyalkylene oxide chain includes a case where only one alkylene oxide is attached. Similarly, (poly) oxyalkylene glycol includes a case where only one alkylene oxide is attached.

In this invention, the manufacturing method of the polycarboxylic acid type copolymer containing the said processes 1-3 is one of the suitable forms, and it follows the following chemical reaction formula about the especially preferable form of the processes 1-3 below. I will explain.
In the said process 1, it is preferable to make methallyl chloride and ethylene glycol react and to obtain ethylene glycol monomethallyl ether (methallyl alcohol 1EO).

In the said process 1, as shown to the said Reaction Formula, ethylene glycol dimethallyl ether (X), methallyl alcohol (W), and water will produce | generate as a by-product.
The product containing methallyl alcohol 1EO obtained in Step 1 is preferably purified by distillation to obtain highly pure methallyl alcohol 1EO. As distillation, distillation under reduced pressure is preferable.
In the distillation step, ethylene glycol and sodium chloride are separated into the bottom layer, and other by-products (X), methallyl alcohol (W), and methallyl alcohol 1EO all have close boiling points. It will be collected in the same way as 1EO. In addition, since the boiling point of methallyl alcohol 1EO is higher than the boiling point (113-115 degreeC) of methallyl alcohol (W), it is easy to distill and purity can be made higher.

In the said process 2, it is preferable to add ethylene oxide (EO) to the distillation refinement | purification mixture of the process 1. Here, a methallyl alcohol n-EO adduct is produced. In Step 2, an internal olefin (Z) in which a double bond of polyethylene glycol (Y) and methallyl alcohol n-EO adduct is thermally transferred is generated in addition to the by-product in Step 1.

In the said process 3, it is preferable to copolymerize the product containing the methallyl alcohol-n-EO obtained in the process 2 and acrylic acid as represented by the following reaction formula. Specifically, it is preferable to obtain a polycarboxylic acid copolymer (polycarboxylic acid polymer) by copolymerizing the methallyl alcohol n-EO adduct containing the by-product of Steps 1 and 2 with acrylic acid. . Such a polycarboxylic acid-based copolymer can be suitably used as, for example, a polycarboxylic acid for a cement admixture.

In the manufacturing method of the polycarboxylic acid-type copolymer of this invention, as mentioned above, manufacturing through a methallyl alcohol-n-EO adduct is preferable. Further, as represented by the following formula, a polycarboxylic acid copolymer is used by using a 3-methyl-3-butenyl monomer (MBN monomer) obtained by adding ethylene oxide to 3-methyl-3-butenyl chloride. The form which manufactures coalescence can also be used.

In the MBN monomer, an example in which ethylene oxide is added as the alkylene oxide to be added is shown, but other alkylene oxides may be used. The chain length of the alkylene oxide is preferably in the range of 1 to 300 as described above, but in the case of an MBN monomer, it is preferably in the same range as described above. That is, the average added mole number is preferably larger to some extent, and is preferably a specific value or more in the following order (a larger numerical value is preferable). That is, 10 or more, 25 or more, 35 or more, 50 or more, 75 or more, 100 or more, 110 or more, 120 or more, 135 or more, 150 or more are preferable. Moreover, it is also preferable that the average added mole number is not too large, and it is preferable that the average added mole number is not more than a specific value in the following order (a smaller numerical value is preferable). That is, 280 or less, 250 or less, 225 or less, and 200 or less are preferable. The smaller the average number of added moles, the lower the hydrophilicity and the lower the effect of repelling the cement particles, so the dispersion performance of the resulting copolymer may be reduced. Copolymerization reactivity may be reduced.
As the halogen compound having an unsaturated bond in the present invention, methallyl chloride and 3-methyl-3-butenyl chloride are particularly suitable. However, a monomer having a long-chain alkylene oxide is produced to produce a long-chain alkylene. When obtaining the polycarboxylic acid-type copolymer which has an oxide, it is more preferable to use methallyl chloride. The reaction formula in the case of adding 3-methyl-3-butenyl alcohol with ethylene oxide is shown below, and the reason why it is more preferable to use methallyl chloride will be described.

As shown in the above formula, in the MBN monomer, in the process of addition reaction of ethylene oxide, the MBN monomer may be conjugated, and a decomposition reaction to isoprene and polyethylene glycol (PEG) may occur. More difficult than the system. In addition, when the MBN monomer is purified by distillation after EO addition, or when the MBN monomer is heated and stored, the MBN monomer needs to be heated when dissolved in a solvent in order to copolymerize with acrylic acid. Decomposition reaction may occur due to heating. Thus, when exposed to a high temperature for a long time (eg, 130 ° C. or more, 40 hours or more), it is decomposed into isoprene and PEG. For example, when ethylene oxide is added up to about n = 150 to make a long chain, PEG, which is a decomposition product, is formed during the addition of ethylene oxide, about 20 to 50% by mass of the entire product. In addition, the addition amount of the MBN monomer needs to be about twice, which may be disadvantageous economically. Accordingly, MBN monomers having an EO chain length of 150 mol or less are preferably used. In addition, it may be difficult to make the chain long, and substantially 75 mol or less of an MBN monomer may be suitably used.

The methallyl monomer, which is one of the most preferred embodiments of the present invention, can be easily made longer because it does not undergo conjugation and does not decompose as does the MBN monomer. Specifically, the EO chain length can be 150 mol or more. A polycarboxylic acid-based copolymer (polycarboxylic acid polymer) having such a long-chain PEG can exhibit very high dispersion performance with respect to the cement composition when used as a cement admixture. There are advantages.

A summary of the synthesis route for the methallyl monomer, which is one of the most preferred embodiments of the present invention, is shown below. In addition, as a result of reacting methallyl chloride and ethylene glycol in Step 1, ethylene glycol dimethallyl ether (X), methallyl alcohol (W) and water are produced as by-products, but methallyl alcohol of (W). Becomes methallyl alcohol-n-EO by EO addition in step 2.

An example of the addition reaction for Step 2 is shown below. As described below, when EO is added, polyethylene glycol (Y) may be generated as a by-product.

The present invention is also a polymer having a (poly) alkylene glycol chain obtained by polymerizing a monomer component containing an unsaturated (poly) alkylene glycol ether monomer obtained by the above production method. The present invention is also a polymer having a (poly) alkylene glycol chain obtained by the above production method.
In the polymer having a (poly) alkylene glycol chain obtained by the above production method, an unsaturated (poly) alkylene glycol diether monomer is incorporated into the polymer. That is, a polymerization reaction occurs with the monomer component during the polymerization, and no unsaturated (poly) alkylene glycol diether monomer is confirmed in the solution after polymerization. A polymer in which such an unsaturated (poly) alkylene glycol diether monomer is incorporated (a polymer having a (poly) alkylene glycol chain) has excellent properties such as excellent dispersion performance and fluidity retention performance of the cement composition. Can be suitably used for various applications.

When a polymer having a (poly) alkylene glycol chain obtained by the above method is obtained using the above steps 1 to 3, the production cost is low, and therefore it is suitably used for various applications. In addition, when unsaturated carboxylic acid is used as a monomer to be copolymerized, when used as a cement admixture, it is excellent in fluidity, water reduction, workability, and additive reduction effect, and the strength and durability of the cured product. And a polycarboxylic acid copolymer that exhibits excellent properties of making it easy to work in the field where it is handled and improving the workability of the cement composition and reducing the addition amount at the same time. it can. Hereinafter, a polycarboxylic acid copolymer will be described as a preferred example of a polymer having a (poly) alkylene glycol chain. However, in a polymer other than the polycarboxylic acid copolymer, the constituent components of the polymer are also described. It can be appropriately selected and applied to various polymers. The ratio of each structural unit constituting the polycarboxylic acid copolymer is preferably the same as the blending ratio of the monomer.

The weight average molecular weight of the polycarboxylic acid copolymer is suitably in the range of 3000 to 300000, preferably in the range of 5000 to 200000, more preferably in the range of 10,000 to 150,000, and still more preferably in the range of 10,000 to 100,000. The range of 20000 to 80000 is most preferable. By selecting such a weight average molecular weight range, a cement admixture exhibiting higher dispersion performance can be obtained.
The weight average molecular weight of the polymer is a weight average molecular weight in terms of polyethylene glycol determined by gel permeation chromatography (hereinafter referred to as “GPC”), and is preferably measured under GPC measurement conditions described later.

The polycarboxylic acid-based copolymer preferably has a number of milliequivalents of carboxyl groups when all the carboxyl groups of the copolymer are converted to an unneutralized type, and is 5.50 meq or less per gram of copolymer. More preferably 0.10 to 5.50 meq / g, still more preferably 0.15 to 4.00 meq / g, particularly preferably 0.20 to 3.50 meq / g, most preferably 0.30 to 3.00 meq / g. The range of g is good.
The number of milliequivalents of carboxyl groups when all the carboxyl groups in the polycarboxylic acid copolymer are converted to an unneutralized type can be calculated as follows. For example, acrylic acid is used as the unsaturated carboxylic acid, and unsaturated (poly) alkylene glycol ether monomer (monomer (i)) / unsaturated carboxylic acid (monomer (ii)) = 90/10 ( When the copolymer is copolymerized at a composition ratio of (mass%), the molecular weight of acrylic acid is 72, so the number of milliequivalents of carboxyl groups per gram of copolymer is (0.1 / 72) × 1000 = 1.39 (meq / G) (Calculation Example 1). For example, when sodium acrylate is used as the monomer (ii) and copolymerization is performed at a composition ratio of monomer (i) / monomer (ii) = 90/10 (mass%), sodium acrylate The molecular weight of acrylic acid is 94, and the molecular weight of acrylic acid is 72. Therefore, the number of milliequivalents of carboxyl groups per 1 g of copolymer is (0.1 / 94) / (0.9 + 0.1 × 72/94) × 1000 = 1.09 (meq / g) (calculation example 2). In addition, when acrylic acid is used at the time of polymerization and the carboxyl group derived from acrylic acid is neutralized with sodium hydroxide after polymerization, the calculation can be performed in the same manner as in Calculation Example 2. Further, for example, sodium methacrylate and sodium acrylate are used as the monomer (ii), and the monomer (i) / sodium methacrylate / sodium acrylate = 90/5/5 (mass%) When polymerized, the molecular weight of methacrylic acid is 86, the molecular weight of sodium methacrylate is 108, the molecular weight of acrylic acid is 72, and the molecular weight of sodium acrylate is 94. Therefore, the number of milliequivalents of carboxyl groups per gram of copolymer is (0.05 / 108 + 0.05 / 94) / (0.9 + 0.05 × 86/108 + 0.05 × 72/94) × 1000 = 1.02 (meq / g) (Calculation Example 3).

The polycarboxylic acid copolymer of the present invention is particularly preferably used as a cement admixture or a concrete admixture. Thus, a cement admixture containing the polycarboxylic acid copolymer is also one of the preferred embodiments of the present invention.
When the cement admixture contains the above-described polycarboxylic acid-based copolymer, the cement admixture can exhibit excellent effects such as dispersion performance, slump retention performance, mortar and concrete durability improvement. In addition, the cement composition comprising the above cement admixture, cement and water as essential components has a viscosity (workability, e.g., ease of kneading when kneading mortar and scoop work in concrete) and fluidity ( (Ease of flow when pouring) can be demonstrated. The technical correlation between the “flow value” (fluidity) indicating the physical properties of the cement composition and the “concrete state” (viscosity) is at least not clear at the present time. For example, when comparing candy candy and yogurt, candy candy is sticky, so if you try to stir it with a spoon, you need a lot of force (high viscosity and poor workability), but on a flat surface. When placed, it flows and spreads thinly. On the other hand, when trying to stir yogurt with a spoon, it can be easily stirred (low viscosity and good workability), but it does not flow and spread even when placed on a flat surface.

The polycarboxylic acid-based copolymer can be used as it is as a main component of a cement admixture, but it is preferable to adjust the pH to 5 or more from the viewpoint of handleability. As described above, the copolymerization reaction is preferably performed at a pH of less than 5, and the pH is preferably adjusted to 5 or more after the copolymerization. The pH can be adjusted using, for example, an alkaline substance such as an inorganic salt such as a monovalent metal or divalent metal hydroxide or carbonate; ammonia; an organic amine; Further, after the reaction is completed, the concentration can be adjusted if necessary. The polycarboxylic acid copolymer may be used as a main component of the cement admixture as it is in the form of an aqueous solution, or may be neutralized with a hydroxide of a divalent metal such as calcium or magnesium. It may be used after being made into a polyvalent metal salt and then dried, or supported on an inorganic powder such as silica fine powder and dried.

The cement admixture essentially comprises the polycarboxylic acid copolymer. The content of the polycarboxylic acid copolymer in the cement admixture is not particularly limited, but is preferably 20% by mass or more, preferably 40% by mass or more of the solid content in the cement admixture, that is, the non-volatile content. More preferably.
In the present invention, the following method is suitable as a method for measuring the solid content of the cement admixture.
(Solid content measurement method)
1. Weigh the aluminum dish.
The solid content to be measured is precisely weighed on the aluminum dish precisely weighed in 2.1.
3. A solid content measurement product precisely weighed in 2 is placed in a dryer adjusted to 130 ° C. in a nitrogen atmosphere for 1 hour.
4. After 1 hour, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes.
5. After 15 minutes, remove from the desiccator and precisely weigh the aluminum dish and the measurement object.
The mass of the aluminum dish obtained in 1 is subtracted from the mass obtained in 6.5, and the solid content is measured by dividing the mass of the fixed part obtained in 2.
The cement admixture may be a combination of two or more copolymers. For example, a combination of two or more copolymers having different ratios of the structural unit (I) derived from the monomer (i) and the structural unit (II) derived from the monomer (ii) A combination of two or more kinds of copolymers having different average added mole numbers of the oxyalkylene group of the structural unit (I) introduced by i) is possible.

It is preferable that the cement admixture contains 1 to 50% by mass of polyalkylene glycol with respect to the copolymer in addition to the polycarboxylic acid copolymer. More preferably, it is 2-50 mass%, More preferably, it is 2-40 mass%, Most preferably, it is good to contain 3-30 mass%. By containing polyalkylene glycol, it becomes a dispersant that can further improve the workability of mortar and concrete. When the content of polyalkylene glycol is less than 1% by mass, the workability improvement effect of mortar and concrete becomes insufficient, while when it exceeds 50% by mass, dispersibility with respect to cement is lowered, which is not preferable.

As the polyalkylene glycol, those having an oxyalkylene group having 2 to 18 carbon atoms are suitable, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. Is good. Furthermore, since the polyalkylene glycol needs to be water-soluble, it is preferable to have at least an oxyalkylene group having a high hydrophilicity, ie, an oxyethylene group having 2 carbon atoms, that is, an oxyethylene group of 90 mol% or more. More preferably, it contains an ethylene group. The repeating unit of the oxyalkylene group may be the same or different. When the oxyalkylene group is in the form of a mixture of two or more, block addition, random addition, alternating addition Any of these additional forms may be used. The terminal group of the polyalkylene glycol is suitably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a (alkyl) phenyl group, but a hydrogen atom is preferred. The average molecular weight of the polyalkylene glycol is preferably in the range of 500 to 200,000, more preferably in the range of 1000 to 100,000, and still more preferably in the range of 2000 to 50000.

Specific examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, and polyethylene polybutylene glycol. The polyalkylene glycol is hydrophilic because it needs to be water-soluble. Polyethylene glycol or polyethylene polypropylene glycol containing a high oxyethylene group as an essential component is preferred, and polyethylene glycol is most preferred.

The cement admixture containing the polyalkylene glycol does not remove, for example, the polyalkylene glycol generated as an impurity in the step 2, but with an unsaturated (poly) alkylene glycol ether monomer (monomer (i)). It is preferable to obtain it by using in step 3. Thus, by using an unsaturated (poly) alkylene glycol ether (monomer (i)) containing polyalkylene glycol as an impurity as a monomer component, the cement admixture containing the polyalkylene glycol can be easily prepared. Can be obtained. In the monomer (i), when the (poly) alkylene glycol to be reacted in Step 1 and the alkylene oxide to be added in Step 2 are the same alkylene group, the halogen of the halide having an unsaturated bond is a hydroxyl group. It can also be obtained by adding an alkylene oxide to an alcohol having an unsaturated bond substituted. For example, it can also be obtained by adding an alkylene oxide to an alcohol (unsaturated alcohol) having an unsaturated bond such as methallyl alcohol, 3-buten-1-ol, or allyl alcohol. In such an addition reaction, a compound having an active hydrogen such as saturated aliphatic alcohols (methanol, ethanol, etc.) other than the alcohol having the unsaturated bond (unsaturated alcohols) and water is present in the reaction system. In addition to the desired unsaturated (poly) alkylene glycol ether monomer, polyalkylene glycol may be by-produced. By removing the by-produced polyalkylene glycol and using the product obtained by the addition reaction as a raw material as it is, the purification process can be simplified, and the obtained cement admixture is a copolymer. And polyalkylene glycol, and the workability of mortar and concrete before curing can be further improved.

The content of the polyalkylene glycol contained as an impurity is suitably 0.5 to 50% by mass with respect to the unsaturated (poly) alkylene glycol ether monomer, but preferably 1 to 40% by mass, 30 mass% is more preferable, and 3-20 mass% is further more preferable. When the proportion of the polyalkylene glycol exceeds 50% by mass, the amount of use as a cement admixture increases because the dispersion performance of the polyalkylene glycol itself is low, which is not preferable.

The cement admixture contains, in addition to the polycarboxylic acid copolymer, an unsaturated (poly) alkylene glycol ether (monomer (i)) having a polyalkylene oxide chain to the copolymer. It is preferable to contain 100 mass%. More preferably, it is 2-100 mass%, More preferably, it is 3-90 mass%, Most preferably, it is good to contain 5-80 mass%. By containing the monomer (i), it becomes a dispersant that can further improve the workability of mortar and concrete. If the content of monomer (i) is less than 1% by mass, the workability improvement effect of mortar and concrete will be insufficient, while if it exceeds 100% by mass, the dispersibility to cement will decrease. It is not preferable.

Such a cement admixture that also contains the monomer (i) is used in the polymer in which the unreacted monomer (i) is produced at the time of copolymerization when the polycarboxylic acid copolymer is obtained. On the other hand, it can be easily obtained by stopping the polymerization reaction at a point of 1 to 100% by mass. Thereby, the obtained product contains the monomer (i) in addition to the copolymer, and can exhibit excellent dispersion performance. The time point at which the polymerization reaction is stopped is preferably when the monomer (i) is 2 to 80% by mass, more preferably 3 to 70% by mass, and still more preferably, with respect to the polymer. Is preferably 5 to 60% by mass. When the polymerization reaction is stopped when the amount of the unreacted monomer (i) is less than 1% by mass with respect to the produced polymer, the resulting cement admixture is insufficient in improving the workability of mortar and concrete. On the other hand, when the polymerization reaction is stopped at a point exceeding 100% by mass, the dispersibility with respect to cement is lowered.

The most preferable form of the cement admixture is one containing both the polyalkylene glycol and the monomer (i) in the above ratio. By containing both of these components, the dispersant becomes extremely excellent in workability of mortar and concrete.

The cement admixture can be used for various hydraulic materials, that is, hydraulic materials other than cement, such as cement and gypsum. And as a concrete example of a hydraulic composition containing a hydraulic material, water and the above cement admixture, and further containing fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) Examples include paste, mortar, concrete, plaster and the like.

Among the hydraulic compositions exemplified above, a cement composition using cement as a hydraulic material is the most common, and a cement composition comprising the cement admixture, cement and water as essential components is also used. This is one of the preferred embodiments of the present invention.

There is no limitation in particular as a cement used in the said cement composition. For example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance and low alkali type of each), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, Super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, belite High-concentration cement), ultra-high-strength cement, cement-based solidified material, eco-cement (city waste incineration ash, sewage sludge incineration ash as a raw material), blast furnace slag, fly ash , Cinder ash, clinker ash Husk ash, silica fume, silica powder, a fine powder and gypsum limestone powder may be added. In addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., as aggregate, siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromic, magnesia, etc. The refractory aggregate can be used.

In the cement composition, the unit water amount per 1 m ³ , the amount of cement used, and the water / cement ratio are not particularly limited, and the unit water amount is 100 to 185 kg / m ³ , the amount of cement used is 250 to 800 kg / m ³ , Water / cement ratio (weight ratio) = 0.1 to 0.7, preferably unit water amount 120 to 175 kg / m ³ , used cement amount 270 to 800 kg / m ³ , water / cement ratio (weight ratio) = 0.15 ~ 0.65 is recommended. As described above, the cement composition of the present invention can be widely used from poor blending to rich blending, and can be used for both high-strength concrete with a large amount of unit cement and poor blended concrete with a unit cement amount of 300 kg / m ³ or less. It is valid. In addition, the cement composition of the present invention has a relatively high water reduction rate, that is, water / cement ratio (weight ratio) = 0.15 to 0.5 (preferably 0.15 to 0.4). Even in a low cement ratio region, it can be used satisfactorily.

The blending ratio of the cement admixture in the cement composition of the present invention is not particularly limited, but when used for mortar or concrete using hydraulic cement, 0.01 to 10% by mass of cement weight, An amount of a ratio of preferably 0.02 to 5% by mass, more preferably 0.05 to 3% by mass may be added. By this addition, various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability are brought about. When the above blending ratio is less than 0.01% by mass, the performance is insufficient. On the contrary, even if a large amount exceeding 10% by mass is used, the effect is practically peaked and disadvantageous from the economical aspect.

The above-mentioned cement composition is effective for concrete for concrete secondary products, concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, sprayed concrete, and the like, and also has high fluidity concrete, self-filling concrete, self It is also effective for mortar and concrete that require high fluidity such as leveling materials.

The cement composition may contain a known cement admixture. Known cement admixtures that can be used are not particularly limited, and various sulfonic acid-based dispersants having a sulfonic acid group in the molecule, and various polycarboxylic acid-based compounds having a polyoxyalkylene chain and a carboxyl group in the molecule. A dispersing agent is mentioned. Examples of the sulfonic acid dispersant include lignin sulfonate; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonate; aminoaryl sulfonic acid-phenol-formaldehyde condensate and the like. A sulfonic acid type | system | group etc. are mentioned. Examples of the polycarboxylic acid-based dispersant include a polyalkylene glycol mono (meth) acrylate ester having a polyoxyalkylene chain in which an alkylene oxide having 2 to 18 carbon atoms is added in an average addition mole number of 2 to 300. A copolymer obtained by copolymerizing a monomer component containing a monomer and a (meth) acrylic acid monomer as essential components; an alkylene oxide having 2 to 3 carbon atoms in an average addition mole number of 2 to 300 The essential component is a polyalkylene glycol mono (meth) acrylate monomer having an added polyoxyalkylene chain, a (meth) acrylic acid monomer and a (meth) acrylic acid alkyl ester. A copolymer obtained by copolymerizing monomer components contained as poly; a polysiloxane having 2 to 300 additions of an average number of moles of alkylene oxide having 2 to 3 carbon atoms; Polyalkylene glycol mono (meth) acrylic acid ester monomer having a xyalkylene chain, (meth) acrylic acid monomer and (meth) allylsulfonic acid (salt) (or vinylsulfonic acid (salt) or p- (Meth) allyloxybenzenesulfonic acid (any of salts)), a copolymer obtained by copolymerizing a monomer component containing three types of monomers as essential components; 3 types of single quantities of polyalkylene glycol mono (meth) acrylate ester monomer having added polyoxyalkylene chain, (meth) acrylic acid monomer and (meth) allylsulfonic acid (salt) (Meth) acrylamide and / or 2- (meth) acrylamide-2-methyl further to a copolymer obtained by copolymerizing a monomer component containing an isomer as an essential component A copolymer obtained by graft polymerization of lopansulfonic acid; a polyethylene glycol mono (meth) acrylic acid ester monomer having a polyoxyalkylene chain in which ethylene oxide is added in an average addition mole number of 5 to 50 and ethylene oxide in an average addition mole number of 1 Polyethylene glycol mono (meth) allyl ether monomer having added polyoxyalkylene chain, (meth) acrylic acid monomer and (meth) allylsulfonic acid (salt) (or p- (meth) allyl) Copolymer obtained by copolymerizing monomer components containing four types of monomers of oxybenzenesulfonic acid (any of salts) as essential components; average addition mole of alkylene oxide having 2 to 18 carbon atoms Poly (alkylene glycol) mono (meth) allylene having a polyoxyalkylene chain added in an amount of 2 to 300 A copolymer obtained by copolymerizing a monomer component containing an ether monomer and a maleic acid monomer as essential components; an alkylene oxide having 2 to 4 carbon atoms in an average addition mole number of 2 to 300 Obtained by copolymerizing a monomer component containing, as essential components, a polyalkylene glycol mono (meth) allyl ether monomer having an added polyoxyalkylene chain and a polyalkylene glycol ester monomer of maleic acid Copolymer: Polyalkylene glycol 3-methyl-3-butenyl ether monomer having a polyoxyalkylene chain obtained by adding 2 to 300 average addition moles of alkylene oxide having 2 to 4 carbon atoms and maleic acid monomer And a copolymer obtained by copolymerizing a monomer component containing a monomer as an essential component. The known cement admixture can be used in combination.

When the known cement dispersant is used, the blending weight ratio between the cement admixture and the known cement admixture is uniquely determined by the difference in the type, blending, and test conditions of the known cement admixture used. Is not determined, but is preferably in the range of 5:95 to 95: 5, more preferably 10:90 to 90:10.
Furthermore, the said cement composition can contain the other well-known cement additive (material) which is illustrated to the following (1)-(20).

(1) Water-soluble polymer substance: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer; methyl Nonionic cellulose ethers such as cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and hydroxypropyl cellulose; polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose A part of or all of the hydroxyl groups of the alkylated or hydroxyalkylated derivatives of the present invention are a hydrophobic substituent having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, a sulfonic acid group or Polysaccharide derivatives substituted with an ionic hydrophilic substituent containing such a salt as a partial structure; yeast glucan, xanthan gum, β-1.3 glucan (both linear and branched chain, one example For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; Copolymers of acrylic acid having groups and quaternary compounds thereof.

(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.
(3) retarder: oxycarboxylic such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and inorganic salts or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. Acids: monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, oligosaccharides such as dextrin, polysaccharides such as dextran, etc. Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin; aminotri (methylenephos Phosphonic acid and derivatives thereof such as phonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts and alkaline earth metal salts thereof etc.

(4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.
(5) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.
(6) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.

(7) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.
(8) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as 2-ethylhexyl ether and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) oxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 − Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylenic alcohol such as tin-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene (Poly) oxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate salts; (poly) oxyethylene stearyl phosphates, etc. Sialic sharp emission alkyl phosphate esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide.

(10) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like.
(11) Amide antifoaming agent: acrylate polyamine and the like.
(12) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.
(13) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.
(14) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

(15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether , Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate, and the like.

(16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives having an alkyl or alkoxy group as a substituent Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionics Surfactant; various amphoteric surfactants.

(17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt, wax and the like.
(18) Rust preventive: nitrite, phosphate, zinc oxide and the like.
(19) Crack reducing agent: polyoxyalkyl ether and the like.
(20) Expansion material: Ettlingite, coal, etc.

Other known cement additives (materials) include, for example, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust inhibitors, colorants, An antifungal agent etc. can be mentioned. The above-mentioned known cement additives (materials) can be used in combination.

In the above cement composition, the following 1) to 7) are particularly preferable embodiments for components other than cement and water.

1) A combination comprising two components, i.e. (i) the cement admixture and (ii) an oxyalkylene-based antifoaming agent. In addition, as a compounding weight ratio of the oxyalkylene type | system | group antifoamer of (ii), the range of 0.01-10 mass% with respect to the cement admixture of (i) is preferable.

2) (i) the above-mentioned cement admixture, (ii) a polyalkylene glycol mono (meth) acrylate ester-based unit having a polyoxyalkylene chain obtained by adding 2 to 300 average addition moles of an alkylene oxide having 2 to 18 carbon atoms. A copolymer comprising a monomer, a (meth) acrylic acid monomer, and a monomer copolymerizable with these monomers (Japanese Patent Publication No. 59-18338, Japanese Patent Laid-Open No. 7-223852, (Iii) (iii) a combination comprising essentially three components of an oxyalkylene antifoaming agent. The blending weight ratio of the cement admixture (i) and the copolymer (ii) is preferably in the range of 5:95 to 95: 5, and more preferably in the range of 10:90 to 90:10. The blending weight ratio of the oxyalkylene antifoaming agent (iii) is preferably in the range of 0.01 to 10% by mass with respect to the total amount of the cement admixture (i) and the copolymer (ii). .

3) A combination comprising essentially two components: (i) the cement admixture, and (ii) a sulfonic acid-based dispersant having a sulfonic acid group in the molecule. Examples of the sulfonic acid dispersant include lignin sulfonate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, polystyrene sulfonate, aminoaryl sulfonic acid-phenol-formaldehyde condensate and the like. An agent or the like can be used. The blending weight ratio of the cement admixture (i) and the sulfonic acid dispersant (ii) is preferably in the range of 5:95 to 95: 5, more preferably in the range of 10:90 to 90:10. preferable.

4) A combination that essentially comprises two components (i) the cement admixture and (ii) lignin sulfonate. The blending weight ratio of the cement admixture (i) and the lignin sulfonate salt (ii) is preferably in the range of 5:95 to 95: 5, and more preferably in the range of 10:90 to 90:10. .

5) A combination comprising two components of (i) the above cement admixture and (ii) a material separation reducing agent. As a material separation reducing agent, various thickeners such as nonionic cellulose ethers, a hydrophobic substituent consisting of a hydrocarbon chain having 4 to 30 carbon atoms as a partial structure and an alkylene oxide having 2 to 18 carbon atoms are added on average. A compound having a polyoxyalkylene chain having 2 to 300 moles added can be used. In addition, as a compounding weight ratio of the cement admixture of (i) and the material separation reducing agent of (ii), the range of 10: 90-99.99: 0.01 is preferable, and 50: 50-99.9: A range of 0.1 is more preferred. A cement composition comprising this combination is suitable as high fluidity concrete, self-filling concrete, and self-leveling material.

6) A combination comprising two components of (i) the cement admixture and (ii) retarder. As the retarder, oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), saccharides such as glucose, sugar alcohols such as sorbitol, phosphonic acids such as aminotri (methylenephosphonic acid), etc. can be used. . The blending weight ratio of the cement admixture (i) and the retarder (ii) is preferably in the range of 50:50 to 99.9: 0.1, and in the range of 70:30 to 99: 1. More preferred.

7) A combination comprising two components of (i) the cement admixture and (ii) an accelerator. As the accelerator, soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfate, formic acid and calcium formate, and the like can be used. The blending weight ratio of the cement admixture (i) and the accelerator (ii) is preferably in the range of 10:90 to 99.9: 0.1, and is preferably in the range of 20:80 to 99: 1. More preferred.

The method for producing an unsaturated (poly) alkylene glycol ether monomer and the method for producing a polymer having a (poly) alkylene glycol chain according to the present invention has the above-described configuration and is suitable for various applications such as a cement admixture. It can be used, the setting time of concrete can be shortened, and the early strength of concrete can be improved.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Production Example 1: Production of ethylene glycol monomethallyl ether (A-1)>
[Reaction process]
A 3 L flask was charged with 1500.0 g (24,17 mol) of ethylene glycol, 420.92 g of 48 wt% sodium hydroxide aqueous solution (5.05 mol of NaOH), and 452.79 g (5.00 mol) of methallyl chloride, and stirred at 60 ° C. For 3 hours and then at 70 ° C. for 3 hours. Precipitation of salt was observed in the flask.
[Dehydration process]
An oil / water separation tube was attached to the flask after the above reaction, and distillation under reduced pressure was performed with oil / water separation of the distillate under stirring to separate 292.34 g of water. The operation pressure was initially 200 mmHg and later lowered to 100 mmHg, and the operation was terminated when the distillate became a uniform layer.
Thereafter, the precipitated salt was filtered off using filter paper (4 μm) to obtain 1709.59 g of filtrate. Further, the salt was washed and filtered with 100.22 g of ethylene glycol to obtain 117.64 g of a cleaning solution. As a result of analysis by gas chromatography, the yield of ethylene glycol monomethallyl ether was 80.2 mol%, and the yield of ethylene glycol dimethallyl ether was 11.8 mol% (calculated on the basis of methallyl chloride).
Further, when the residual water content was analyzed by the Karl Fischer method, it was 0.84% by mass.
[Distillation process]
A total of 1798.28 g of the reaction solution and the washing solution recovered in the previous step were charged to the bottom of the distillation column to purify ethylene glycol monomethallyl ether. As an distillation apparatus, using an Oldershaw (30 mmφ, filled with Sruzer packing, equivalent to 30 theoretical plates), distillation was performed at a top pressure of 45 mmHg, a reflux ratio of 10, and a bottom temperature of 100 ° C. to 127 ° C. 318.17 g of methallyl ether was obtained. As a result of analysis, the water content was 0.06% by mass, and the ethylene glycol dimethallyl ether content was 0.47% by mass.

<Production Example 2: Production of (X-1) in Diether Form>
The operation of adding 300 g of water to 82.9 g of a fraction having a distillation rate of 22% to 26% in the distillation and stirring and removing the aqueous layer by oil-water separation was repeated three times to obtain 27.4 g of ethylene glycol dimethallyl ether. .
Analysis of the above process was performed with the following apparatus.
Gas chromatography apparatus: GC-15A manufactured by Shimadzu, J & W capillary column DB-1 (0.53 mmφ × 30 m)
Conditions: Holding at 40 ° C. for 5 min, heating at 10 ° C./min, holding at 200 ° C. for 5 min Moisture content measuring device: MK-510 manufactured by Kyoto Electronics Industry Co., Ltd. (KEM)
Standard sample: Karl Fischer SS manufactured by Mitsubishi Chemical Corporation

The GPC measurement conditions are as follows.
Column used: TSK guard column SWXL manufactured by Tosoh Corporation
TSKgel G4000SWXL
TSKgel G3000SWXL
TSKgel G2000SWXL connected in this order.
Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a solution of 6001 g of acetonitrile and 10999 g of water and adjusting the pH to 6.0 with acetic acid was used.
Sample: A polymer aqueous solution dissolved in the eluent so that the polymer concentration is 0.5% by mass.
Sample injection amount: 100 μL
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Detector: Waters 2414 RI detector System: Waters alliance 2695
Analysis software: Waters Emper2 (standard package / GPC option)
Standard material for preparing a calibration curve: polyethylene glycol [peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 11840, 6450, 4250, 1470]
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of the above polyethylene glycol.

<Production Example 3: Production of methallyl alcohol 10EO>
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 95.1 g of the reaction product (A-1) ethylene glycol monomethallyl ether obtained in Production Example 1, an addition reaction catalyst As a solution, 0.21 g of sodium hydroxide was charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 150 ° C. in a nitrogen atmosphere. Then, 325 g of ethylene oxide was introduced into the reactor while maintaining 150 ° C. under a safe pressure, and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction. The obtained reaction product (hereinafter referred to as M-1) was an unsaturated polyalkylene glycol ether monomer (hereinafter referred to as MLA-10) obtained by adding an average of 10 moles of ethylene oxide to methallyl alcohol. ) And diether (X-1) and by-product (Y-1) and by-product (Z-1). The by-product (Y-1) is a water-soluble polyalkylene glycol (polyethylene glycol), and the by-product (Z-1) is liquid chromatography using a differential refraction (RI) detector (hereinafter referred to as “LC (RI ) "Or simply referred to as" LC "). The analysis results of the reaction product M-1 are shown in Table 1. The LC chart of the reaction product (M-1) is shown in FIG. In FIG. 1, the peak near 22 minutes indicates MLA-10, and the peak near 27 minutes indicates Z-1.

The LC measurement conditions for the reaction product are as follows.
Column used: Inertsil guard column manufactured by GL Science Co., Ltd. 1 Inertsil ODS-25 μm 4.6 mm × 250 mm 3 eluent: Water was added to acetic acid 52.5 g and sodium acetate trihydrate 3.75 g to make 9000 g, and acetonitrile What added 6000g was used.
Sample: Adjusted with the above eluent so that the reaction product concentration is 1.0 mass%.
Sample injection amount: 100 μL
Flow rate: 0.6 mL / min Column temperature: 40 ° C
Detector: Waters 2414 RI detector

Hereinafter, the quantification of diether (X) is carried out by preparing a calibration curve by LC using the diether synthesized in the above Production Example 2 (impurities are not detected and the purity is 100%). Mass% was calculated. LC represents liquid chromatography, and the measurement conditions are as described above.
About the said by-product (Z), content was computed from the area ratio of LC mentioned above.
(Z-1)% = [(Z-1 area) / MLA-10 area] × 100
(Z-2)% = [(Z-2 area) / MLA-50 area] × 100
(Z-3)% = [(Z-3 area) / MLA-120 area] × 100

The by-product (Y) was quantified by the following GPC.
<Measurement conditions for polyalkylene glycol (Y)>
Column used: Shodex GF-1G 7B Showa Denko GF-310 HQ
Eluent: water / acetonitrile = 98/2 (mass%)
Sample: A sample prepared by adjusting the concentration of the reaction product to 0.1% by mass with the above eluent.
Sample injection amount: 250 μL
Flow rate: 1 mL / min Column temperature: 40 ° C
Detector: Waters 2414 RI detector System: Waters alliance 2695
Analysis software: Waters Emper2 (standard package / GPC option)
A calibration curve was prepared under the above measurement conditions for each of the standard materials for creating a calibration curve: polyethylene glycol [peak top molecular weight (Mp) 11840, 6450, 1470], and mass% with respect to polyethylene glycol monomethacrylic ether was calculated.
(Y-3) with respect to MLA120 in M-3 of Production Example 5 was quantified with a calibration curve of PEG of Mp 11840.
(Y-2) against MLA50 in M-2 of Production Example 4 was quantified with a calibration curve of PEG of Mp 6450.
(Y-1) with respect to MLA10 in M-1 of Production Example 3 was quantified using a calibration curve of PEG of Mp 1470.

<Production Example 4: Production of methallyl alcohol 50EO>
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 450.7 g of the reaction product (M-1) obtained in Production Example 3 and 48% hydroxylation as an addition reaction catalyst A sodium aqueous solution (0.36 g) was charged, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring and flowing nitrogen, and the inside of the reaction vessel was depressurized to 6.65 × 10 ³ Pa (50 Torr) using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 130 ° C. in a nitrogen atmosphere. Then, 1550 g of ethylene oxide was introduced into the reactor while maintaining 130 ° C. under a safe pressure, and the reaction was terminated by maintaining the temperature until the alkylene oxide addition reaction was completed. The obtained reaction product (hereinafter referred to as M-2) was an unsaturated polyalkylene glycol ether monomer (hereinafter referred to as MLA-50) obtained by adding 50 moles of ethylene oxide to methallyl alcohol on average. A diether (X-2) and a by-product (Y-2) and a by-product (Z-2) are included. The by-product (Y-2) contains water-soluble polyalkylene glycol (polyethylene glycol), and the by-product (Z-2) is a peak observed around 30 minutes in LC (RI). The analysis results of the reaction product M-2 are shown in Table 1. The LC chart of the reaction product (M-2) is shown in FIG. In FIG. 2, the peak near 24 minutes indicates MLA-50, and the peak near 30 minutes indicates Z-2.

<Production Example 5: Production of production of methallyl alcohol 120EO>
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 849 g of the reaction product (M-2) obtained in Production Example 4, 48% sodium hydroxide aqueous solution as an addition reaction catalyst 0.48 g was charged, and the inside of the reaction vessel was purged with nitrogen under stirring, and then the temperature was raised to 100 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring and flowing nitrogen, and the inside of the reaction vessel was depressurized to 6.65 × 10 ³ Pa (50 Torr) using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 130 ° C. in a nitrogen atmosphere. Then, 1151 g of ethylene oxide was introduced into the reactor while maintaining 130 ° C. under a safe pressure, and the reaction was terminated by maintaining the temperature until the alkylene oxide addition reaction was completed. The obtained reaction product (hereinafter referred to as M-3) was an unsaturated polyalkylene glycol ether monomer (hereinafter referred to as MLA-120) obtained by adding an average of 120 moles of ethylene oxide to methallyl alcohol. And diether (X-3) and by-product (Y-3) and by-product (Z-3). The by-product (Y-3) contains water-soluble polyalkylene glycol (polyethylene glycol), and the by-product (Z-3) is a peak observed at around 35 minutes in LC (RI). The analysis results of the reaction product M-3 are shown in Table 1. The LC chart of the reaction product (M-3) is shown in FIG. In FIG. 3, the peak near 27 minutes indicates MLA-120, and the peak near 35 minutes indicates Z-3.

<Production Example 6: Production of methallyl alcohol 135EO>
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 3023 g of the reaction product (M-2) obtained in Production Example 4, 48% sodium hydroxide aqueous solution as an addition reaction catalyst 2.07 g was charged, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring and flowing nitrogen, and the inside of the reaction vessel was depressurized to 6.65 × 10 ³ Pa (50 Torr) using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 130 ° C. in a nitrogen atmosphere. Then, 4976 g of ethylene oxide was introduced into the reactor while maintaining 130 ° C. under a safe pressure, and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction. The resulting reaction product (hereinafter referred to as M-4) was an unsaturated polyalkylene glycol ether monomer (hereinafter referred to as MLA-135) obtained by adding an average of 135 moles of ethylene oxide to methallyl alcohol. And diether (X-4) and by-product (Y-4) and by-product (Z-4). The by-product (Y-4) contains water-soluble polyalkylene glycol (polyethylene glycol), and the by-product (Z-4) is a peak observed around 38 minutes in LC (RI). The analysis results of the reaction product M-4 are shown in Table 1. The LC chart of the reaction product (M-4) is shown in FIG. In FIG. 4, the peak near 30 minutes indicates MLA-135, and the peak near 38 minutes indicates Z-4. As the details of the peak showing MLA-135, the retention time (minutes) is 29.823 minutes, the peak area is 125952353 μV seconds (the peak area ratio (% area) is 94.02%), The height was 869382 μV. As for the details of the peak indicating Z-4, the retention time is 39.986 minutes, the peak area is 8017627 μV seconds (the peak area ratio (% area) is 5.98%), The height was 41343 μV.
In the following Table 1, the content ratio of diether (X), by-products (Y) and (Z) is the ratio (part) of each impurity to 100 parts of unsaturated alcohol.

<Production Example 7: Production of methallyl alcohol 150EO>
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 2724 g of the reaction product (M-2) obtained in Production Example 4, 48% sodium hydroxide aqueous solution as an addition reaction catalyst 2.20 g was charged, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring and flowing nitrogen, and the inside of the reaction vessel was depressurized to 6.65 × 10 ³ Pa (50 Torr) using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 130 ° C. in a nitrogen atmosphere. Then, 5276 g of ethylene oxide was introduced into the reactor while maintaining 130 ° C. under a safe pressure, and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction. The obtained reaction product (hereinafter referred to as M-5) was an unsaturated polyalkylene glycol ether monomer (hereinafter referred to as MLA-150) obtained by adding an average of 150 moles of ethylene oxide to methallyl alcohol. And diether (X-5) and by-product (Y-5) and by-product (Z-5). The by-product (Y-5) contains water-soluble polyalkylene glycol (polyethylene glycol), and the by-product (Z-5) is a peak observed around 40 minutes in LC (RI). The analysis results of the reaction product M-5 are shown in Table 1.
In the following Table 1, the content ratio of diether (X), by-products (Y) and (Z) is the ratio (part) of each impurity to 100 parts of unsaturated alcohol.

<Production Example 8: Production of cement dispersant 1 of the present invention>
Reaction obtained in Production Example 4 as ion-exchanged water 102 g and unsaturated polyalkylene glycol ether monomer in a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device 198 g of product (M-3) and 0.14 g of acrylic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 58 ° C., 12.85 g of a 2% aqueous hydrogen peroxide solution was added. While maintaining the inside of the reaction vessel at 58 ° C., an acrylic acid aqueous solution consisting of 8.09 g of acrylic acid and 16,32 g of ion exchange water was dropped over 3 hours, and at the same time, L-ascorbine was added to 36.47 g of ion exchange water. An aqueous solution in which 0.666 g of acid and 0.369 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a cement dispersant 1 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 43400.
In the method for producing a polymer having a (poly) alkylene glycol chain, the unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether) is an unsaturated (poly) alkylene glycol ether monomer. According to Table 1, from Table 1, (100 parts of unsaturated polyalkylene glycol ether obtained by adding an average of 120 moles of ethylene oxide to methallyl alcohol) + (0.01 part of ethylene glycol dimethallyl ether) = 100.01, 0.01 % Will be included.

<Production Example 9: Production of comparative cement dispersant 1>
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 198 g of unsaturated polyalkylene glycol ether in which 102 g of ion-exchanged water and 120 mol of ethylene oxide on average were added to methallyl alcohol. Then, 0.14 g of acrylic acid was charged, and the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 58 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 58 ° C., 12.85 g of a 2% aqueous hydrogen peroxide solution was added. Acrylic acid aqueous solution consisting of 8.09 g of acrylic acid and 16.32 g of ion exchange water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 36.47 g of ion exchange water. An aqueous solution in which 0.666 g of acid and 0.369 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a comparative cement dispersant 1 comprising a polymer aqueous solution having a weight average molecular weight of 40,300.

<Production Example 10: Production of cement dispersant 2 of the present invention>
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 198 g of unsaturated polyalkylene glycol ether in which 102 g of ion-exchanged water and 120 mol of ethylene oxide on average were added to methallyl alcohol. Then, 0.04 g of ethylene glycol dimethallyl ether and 0.14 g of acrylic acid were charged as unsaturated polyalkylene glycol-based diether monomers, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 58 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 58 ° C., 12.85 g of a 2% aqueous hydrogen peroxide solution was added. Acrylic acid aqueous solution consisting of 8.09 g of acrylic acid and 16.32 g of ion exchange water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 36.47 g of ion exchange water. An aqueous solution in which 0.666 g of acid and 0.369 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain the cement dispersant 2 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 41300. In the above method for producing a polymer having a (poly) alkylene glycol chain, an unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether 0.04 g) is an unsaturated (poly) alkylene glycol. As an ether monomer, (unsaturated polyalkylene glycol ether 198 g obtained by adding 120 mol of ethylene oxide on average to methallyl alcohol) + (ethylene glycol dimethallyl ether 0.04 g) = 0.02% by mass in 198.04 g Will be.

[Examples 1 and 2 and Comparative Examples 1 and 2]
<Mortar test>
(Solid content measurement)
The polymer used for the performance test was measured for non-volatile content by the following procedure, and the concentration was calculated using the non-volatile content as a cement dispersant.
About 0.5 g of an aqueous cement dispersant solution was weighed into an aluminum cup, and about 1 g of ion exchange water was added to spread it uniformly. This was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and the nonvolatile content was measured from the mass difference before drying.
(Adjustment of cement admixture)
A predetermined amount of the polymer aqueous solution was weighed, 10% by mass of the antifoaming agent MA404 (Pozoris product) was added to the polymer in solid form, and ion-exchanged water was added to make 210 g, which was sufficiently uniformly dissolved. .
(Contains mortar)
The mortar formulation was C / S / W = 600/1350/210 (g). However,
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: ISO standard sand (made by Cement Association)
W: Cement admixture (mortar experimental environment)
The experimental environment was a temperature of 20 ° C. ± 1 ° C. and a relative humidity of 60% ± 10%.
(Measurement of flow value)
600 g of the cement and 210 g of the cement admixture were kneaded from a Hobart type mortar mixer (model number N-50: manufactured by Hobart Co., Ltd.) at a low speed from 30 seconds, and then 1350 g of the ISO sand was added to the cement paste over 30 seconds. Next, after kneading at high speed for 30 seconds, the rotation was stopped and the mortar on the wall of the kettle was scraped off over 15 seconds. The mixture was further left for 75 seconds and then kneaded at a high speed for 60 seconds to adjust the mortar.
Half of the adjusted mortar was packed into a flow cone (described in JIS R5201) placed on a horizontal rotary table, and pierced 15 times using a stick. In addition, the mortar was filled to the full extent of the flow cone, and pierced 15 times with a stick. Thereafter, the flow cone filled with mortar was gently lifted vertically, the major axis (mm) and minor axis (mm) of the mortar spread on the table were measured, and the average value was taken as the mortar zero stroke flow value. Furthermore, after rotating the rotary table 15 times at a speed of once per second, the major axis (mm) and minor axis (mm) of the mortar spread on the table were measured, and the average value was calculated as the flow value of 15 mortars. It was.
(Measurement of mortar air volume)
About 200 mL of mortar was packed in a 500 mL glass graduated cylinder, struck with a round bar having a diameter of 8 mm, and the container was vibrated to remove coarse bubbles. Furthermore, after adding about 200 mL of mortar and removing bubbles in the same manner, the volume and mass were measured, and the amount of air was calculated from the mass and the density of each material.
(Mortar test results)
Table 2 shows the results of a mortar test conducted using the polymer of the present invention and a comparative polymer.

From Table 2, the cement dispersant 1 of the present invention obtained by using ethylene glycol monomethallyl ether obtained from the reaction of methallyl chloride and ethylene glycol as a starting material and an unsaturated alkylene glycol diether monomer were added. The synthesized cement dispersant 2 of the present invention has the same addition amount as that of the comparative cement dispersant 1 obtained by polymerizing an unsaturated alkylene glycol ether monomer not containing an unsaturated alkylene glycol diether monomer. It can be seen that the flow value is high at (0.145% by mass) (Examples 1 and 2 and Comparative Example 1) and the dispersion performance is excellent. Further, when compared at the same flow value (220 mm) (Examples 1 and 2 and Comparative Example 2), it can be seen that the dispersants 1 and 2 of the present invention can reduce the addition amount by 6.5% compared to the comparative cement dispersant 1. .

[Examples 3 and 4 and Comparative Example 3]
<Concrete test>
The concrete composition was adjusted using the cement dispersants 1 and 2 and the comparative cement dispersant 1 obtained as described above, and the slump flow value, air amount, and compressive strength were measured by the following methods. In addition, the material used in the test, the forced kneading mixer, and the measuring instruments are conditioned under the test temperature atmosphere so that the temperature of the concrete composition is 20 ° C. The kneading and each measurement are performed at the test temperature. Performed under atmosphere. The results are shown in Table 3 below.

<Concrete test mix>
Unit cement amount: 573.3 Kg / m ³
Unit water amount: 172.0 Kg / m ³ (including admixtures such as polymer and antifoaming agent)
Unit fine bone agent amount: 737.2 Kg / m ³
Unit coarse bone amount: 866.0 Kg / m ³
Water / cement ratio (W / C): 30.0%
Aggregate amount ratio (s / a): 47.0%
Cement: Taiheiyo Cement Co., Ltd. Ordinary Portland cement fine bone agent: A mixture of Kimitsu mountain sand and Kakegawa water-based agate sand 3/7 Coarse bone agent: Ome crushed stone

<Adjustment of concrete composition>
Each material was weighed so that the amount of kneading became 30 L depending on the concrete raw material and blending, and the material was kneaded by the method described below using a pan mixer.
First, the fine aggregate was kneaded for 10 seconds, then cement was added and kneaded for 10 seconds. Thereafter, a predetermined amount of tap water containing a cement admixture was added and kneaded for 30 to 90 seconds. After that, coarse aggregate was further added and kneaded for 90 seconds to obtain a concrete composition. In the evaluation test, the kneading start time after adding tap water containing a cement admixture was set to zero minutes.

<Adjustment of cement admixture>
It adjusted using the cement dispersing agent and the antifoamer. As the cement dispersant, any one of the cement dispersants 1 and 2 and the comparative cement dispersant 1 was used. The required amount of cement dispersant was calculated using the amount of non-volatile content in the cement dispersant measured by the following method. A commercially available oxyalkylene-based antifoaming agent was used as the antifoaming agent, and the air amount was adjusted to 1.5 ± 0.5 vol%.

<Measurement of non-volatile content>
About 0.5 g of the polymer aqueous solution was measured in an aluminum cup, and about 1 g of ion-exchanged water was added to spread it uniformly. This was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and the nonvolatile content was calculated from the weight difference before and after drying.
<Evaluation test items and measurement method>
Slump flow value: JIS-A-1101
Compressive strength: JIS-A-1108 (specimen preparation: JIS-A-1132)
Air volume: JIS-A-1128

The results of each evaluation test are shown in Table 3 below. From Table 3, the cement dispersant 1 of the present invention obtained by using ethylene glycol monomethallyl ether obtained from the reaction of methallyl chloride and ethylene glycol as a starting material and the addition of unsaturated alkylene glycol diether phosphor are synthesized. The cement dispersant 2 of the present invention was obtained by polymerizing an unsaturated alkylene glycol ether monomer that does not contain an unsaturated alkylene glycol ether monomer that does not contain an unsaturated alkylene glycol diether monomer. It can be seen that the flow value and compressive strength are high (Examples 3 and 4 and Comparative Example 3) at the same addition amount (0.18% by mass) as compared with Comparative Cement Dispersant 1 (Examples 3 and 4 and Comparative Example 3).

<Production Example 11: Production of cement dispersant 3 of the present invention>
Reaction obtained in Production Example 6 as 137 g of ion-exchanged water and unsaturated polyalkylene glycol ether monomer in a glass reactor equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube and reflux cooling device 265 g of product (M-4) and 0.48 g of acrylic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. With the inside of the reaction vessel kept at 58 ° C., 15.32 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution consisting of 9.3 g of acrylic acid and 22.82 g of ion-exchanged water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.62 g of ion-exchanged water. An aqueous solution in which 0.793 g of acid and 0.583 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a cement dispersant 3 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 53,900.
In the component method of the polymer having a (poly) alkylene glycol chain, the unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether) is an unsaturated (poly) alkylene glycol ether monomer. As Table 1, from Table 1, (unsaturated polyalkylene glycol ether 100 parts of an average of 135 moles of ethylene oxide added to methallyl alcohol) + (ethylene glycol dimethallyl ether 0.009 part) = 100.000 parts 009% will be included.

<Production Example 12: Production of cement dispersant 4 of the present invention (diether addition)>
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 137 g of ion-exchanged water and 265 g of unsaturated polyalkylene glycol ether obtained by adding 135 mol of ethylene oxide on average to methallyl alcohol Then, 0.048 g of ethylene glycol dimethallyl ether and 0.48 g of acrylic acid were added as unsaturated polyalkylene glycol-based diether monomers, the inside of the reactor was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. . With the inside of the reaction vessel kept at 58 ° C., 15.32 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution consisting of 9.3 g of acrylic acid and 22.82 g of ion-exchanged water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.62 g of ion-exchanged water. An aqueous solution in which 0.793 g of acid and 0.583 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a cement dispersant 4 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 52,000.
In the component method of the polymer having a (poly) alkylene glycol chain, the unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether 0.048 g) is an unsaturated (poly) alkylene glycol type. As an ether monomer, 0.018% is contained in (unsaturated polyalkylene glycol ether 265 g obtained by adding an average of 135 moles of ethylene oxide to methallyl alcohol) + (ethylene glycol dimethallyl ether 0.0048 g) = 265.048 g. It will be.

<Production Example 13: Production of comparative cement dispersant 2 (without diether)>
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 137 g of ion-exchanged water and 265 g of unsaturated polyalkylene glycol ether obtained by adding 135 mol of ethylene oxide on average to methallyl alcohol Then, 0.48 g of acrylic acid was charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. With the inside of the reaction vessel kept at 58 ° C., 15.32 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution consisting of 9.3 g of acrylic acid and 22.82 g of ion-exchanged water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.62 g of ion-exchanged water. An aqueous solution in which 0.793 g of acid and 0.583 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain Comparative Cement Dispersant 2 comprising a polymer aqueous solution having a weight average molecular weight of 50600.

<Production Example 14: Production of cement dispersant 5 of the present invention>
Reaction obtained in Production Example 7 as ion-exchanged water 137 g and unsaturated polyalkylene glycol ether monomer in a glass reactor equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube and reflux cooling device 266 g of product (M-5) and 0.48 g of acrylic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. With the inside of the reaction vessel kept at 58 ° C., 13.85 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution composed of 8.4 g of acrylic acid and 23.80 g of ion exchange water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.69 g of ion exchange water. An aqueous solution in which 0.717 g of acid and 0.588 g of 3-mercaptopropionic acid were dissolved was added dropwise over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a cement dispersant 5 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 51,000.
In the component method of the polymer having a (poly) alkylene glycol chain, the unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether) is an unsaturated (poly) alkylene glycol ether monomer. As a product, from Table 1, 100 parts of (unsaturated polyalkylene glycol ether obtained by adding an average of 150 mol of ethylene oxide to methallyl alcohol) + (0.008 part of ethylene glycol dimethallyl ether) = 100.008 parts 008% will be included.

<Production Example 15: Production of cement dispersant 6 of the present invention (addition of diether)>
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 266 g of ion-exchanged water and 266 g of unsaturated polyalkylene glycol ether obtained by adding 150 mol of ethylene oxide on average to methallyl alcohol Then, 0.043 g of ethylene glycol dimethallyl ether and 0.48 g of acrylic acid were added as unsaturated polyalkylene glycol-based diether monomers, the inside of the reactor was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. . With the inside of the reaction vessel kept at 58 ° C., 13.85 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution composed of 8.4 g of acrylic acid and 23.80 g of ion exchange water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.69 g of ion exchange water. An aqueous solution in which 0.717 g of acid and 0.588 g of 3-mercaptopropionic acid were dissolved was added dropwise over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain a cement dispersant 6 of the present invention comprising a polymer aqueous solution having a weight average molecular weight of 50000.
In the component method of the polymer having a (poly) alkylene glycol chain, the unsaturated (poly) alkylene glycol diether monomer (ethylene glycol dimethallyl ether 0.043 g) is an unsaturated (poly) alkylene glycol type. As an ether monomer, 0.016% is contained in (unsaturated polyalkylene glycol ether 266 g obtained by adding an average of 150 mol of ethylene oxide to methallyl alcohol) + (ethylene glycol dimethallyl ether 0.0043 g) = 266.043 g. It will be.

<Production Example 16: Production of comparative cement dispersant 3 (without diether)>
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 266 g of ion-exchanged water and 266 g of unsaturated polyalkylene glycol ether obtained by adding 150 mol of ethylene oxide on average to methallyl alcohol Then, 0.48 g of acrylic acid was charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and ripened to 58 ° C. in a nitrogen atmosphere. With the inside of the reaction vessel kept at 58 ° C., 13.85 g of a 2% hydrogen peroxide aqueous solution was added. An acrylic acid aqueous solution composed of 8.4 g of acrylic acid and 23.80 g of ion exchange water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 48.69 g of ion exchange water. An aqueous solution in which 0.717 g of acid and 0.588 g of 3-mercaptopropionic acid were dissolved was added dropwise over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature to obtain Comparative Cement Dispersant 3 comprising a polymer aqueous solution having a weight average molecular weight of 48100.

[Examples 5, 6, 7, 8 and Comparative Examples 4, 5]
<Concrete test (MLA-135 polymer and MLA150 polymer)>
The concrete composition was adjusted using the cement dispersants 3, 4, 5, 6 and the comparative cement dispersants 3, 4 obtained as described above, and the slump flow value, air amount, and compressive strength were adjusted by the following methods. It was measured. In addition, the material used in the test, the forced kneading mixer, and the measuring instruments are conditioned under the test temperature atmosphere so that the temperature of the concrete composition is 20 ° C. The kneading and each measurement are performed at the test temperature. Performed under atmosphere. The results are shown in Table 4 and Table 5 below.

<Concrete test mix>
Unit cement amount: 491.0 Kg / m ³
Unit water amount: 172.0 Kg / m ³ (including admixtures such as polymer and antifoaming agent)
Unit fine bone agent amount: 768.0 Kg / m ³
Unit coarse bone amount: 895.0 Kg / m ³
Water / cement ratio (W / C): 35.0%
Aggregate amount ratio (s / a): 47.0%
Cement: Taiheiyo Cement Co., Ltd. Ordinary Portland cement fine bone agent: A mixture of Kimitsu mountain sand and Kakegawa water-based agate sand 3/7 Coarse bone agent: Ome crushed stone

<Adjustment of concrete composition>
Each material was weighed so that the amount of kneading became 30 L depending on the concrete raw material and blending, and the material was kneaded by the method described below using a pan mixer.
First, fine aggregate, cement, and coarse aggregate were kneaded together for 10 seconds. Thereafter, a predetermined amount of tap water containing a cement admixture was added and kneaded for 60 seconds to obtain a concrete composition. In the evaluation test, the kneading start time after adding tap water containing a cement admixture was set to zero minutes.

<Adjustment of cement admixture>
It adjusted using the cement dispersing agent and the antifoamer. As the cement dispersant, one of cement dispersants 3, 4, 5, 6 and comparative cement dispersants 3, 4 was used. The required amount of cement dispersant was calculated using the amount of non-volatile content in the cement dispersant measured by the following method. A commercially available oxyalkylene-based antifoaming agent was used as the antifoaming agent, and the air amount was adjusted to 1.0 ± 0.5 vol%.

<Measurement of non-volatile content>
About 0.5 g of the polymer aqueous solution was measured in an aluminum cup, and about 1 g of ion-exchanged water was added to spread it uniformly. This was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and the nonvolatile content was calculated from the weight difference before and after drying.
<Evaluation test items and measurement method>
Slump flow value: JIS-A-1101
Compressive strength: JIS-A-1108 (specimen preparation: JIS-A-1132)
Air volume: JIS-A-1128

From Table 4, the cement dispersant 3 of the present invention obtained using ethylene glycol monomethallyl ether obtained from the reaction of methallyl chloride and ethylene glycol as a starting material and an unsaturated alkylene glycol diether monomer were added. The synthesized cement dispersant 4 of the present invention has the same amount of addition as compared with the comparative cement dispersant 3 obtained by polymerizing an unsaturated alkylene glycol ether monomer not containing an unsaturated alkylene glycol diether monomer. It can be seen that the flow value and the compressive strength are high at (0.15% by mass) (Examples 5 and 6 and Comparative Example 5) and the dispersion performance and strength development performance are excellent.
From Table 5, the cement dispersant 5 of the present invention obtained using ethylene glycol monomethallyl ether obtained from the reaction of methallyl chloride and ethylene glycol as a starting material and an unsaturated alkylene glycol diether monomer were added. The synthesized cement dispersant 6 of the present invention has the same amount of addition as compared with the comparative cement dispersant 4 obtained by polymerizing an unsaturated alkylene glycol ether monomer not containing an unsaturated alkylene glycol diether monomer. It can be seen that the flow value and the compressive strength are high at (0.15% by mass) (Examples 7 and 8 and Comparative Example 6) and the dispersion performance and strength development performance are excellent.

Production Examples 17 to 20 and Reference Production Example 1 are shown below.
The analysis of the compounds produced in Production Examples 17 to 20 and Reference Production Example 1 was performed using the following apparatus.
Gas chromatography apparatus: GC-15A manufactured by Shimadzu, J & W capillary column DB-1 (0.53 mmφ × 30 m)
Conditions: Holding at 40 ° C. for 5 min, heating at 10 ° C./min, holding at 200 ° C. for 5 min Moisture content measuring device: MK-510 manufactured by Kyoto Electronics Industry Co., Ltd. (KEM)
Standard sample: Karl Fischer SS manufactured by Mitsubishi Chemical Corporation

Production Example 17
Production of ethylene glycol methallyl ether using new ethylene glycol (reaction process)
A 3 L flask was charged with 1500.0 g (24.17 mol) of ethylene glycol, 420.92 g of 48% by weight aqueous sodium hydroxide (5.05 mol of NaOH), and 452.79 g (5.00 mol) of methallyl chloride. The reaction was carried out at 3 ° C. for 3 hours and then at 70 ° C. for 3 hours. Solid precipitation was observed in the flask. The yield of ethylene glycol monomethallyl ether at the end of the reaction was 85.6 mol% based on the raw material methallyl chloride. The yield of ethylene glycol monomethallyl ether based on ethylene glycol used in the reaction was 17.7 mol%.
(Moisture loss process / solid-liquid separation process)
An oil / water separation tube was attached to the flask after the above reaction, and distillation under reduced pressure was performed with oil / water separation of the distillate under stirring to separate 292.34 g of water. The operation pressure was initially 200 mmHg and later lowered to 100 mmHg, and the dehydration operation was completed when the distillate became a uniform layer.
The precipitated solid matter was separated from the residual slurry after the dehydration operation using a filter paper (No. 5B, 4 μm) to obtain 1709.59 g of filtrate. Further, the solid on the filter paper was washed with 100.22 g (1.61 mol) of ethylene glycol, and the filtrate was obtained by combining 117.64 g of the obtained washing solution and the previous filtrate. At this time, the separated salt was 278.34 g. As a result of gas chromatography analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 80.2 mol%, and the yield of ethylene glycol dimethallyl ether was 11.8 mol% (calculated on the basis of raw material methallyl chloride). . The residual water content was analyzed by the Karl Fischer method and found to be 0.84% by mass.
(Separation process)
1798.28 g of the filtrate obtained in the above step was charged into the bottom of the distillation column to purify ethylene glycol monomethallyl ether. As a distillation facility, distillation was performed under the conditions of a top pressure of 45 mmHg and a bottom temperature of 100 ° C. to 127 ° C. using an apparatus corresponding to a tower diameter of 30 mmφ, regular packing material, and a theoretical plate number of 30 plates. At the beginning of the distillation, the residual water was concentrated and the tower top condensate was separated into two layers, so that 17.25 g of the aqueous layer was separated by oil / water separation. Thereafter, since the condensate became uniform, distillation was performed at a reflux ratio of 10 to obtain 318.17 g of a distillate containing ethylene glycol monomethallyl ether as a main component. As a result of analysis of the distillate, the water content was 0.06% by mass, and the ethylene glycol dimethallyl ether content was 0.47% by mass. In addition, ethylene glycol containing salt as a distillation residue (1289.9 g as a pure component) was recovered.

Production Example 18
Production of ethylene glycol methallyl ether using the ethylene glycol recovered in Production Example 17 (reaction process)
Ethylene glycol recovered in the distillation step of Production Example 17 was added to a pure content of 1102.5 g (17.76 mol) and 399.44 g (6.44 mol) of new ethylene glycol. In place of 0.0 g, 490.91 g (NaOH 5.05 mol) of 48 mass% sodium hydroxide solution was charged and heated to 60 ° C. with stirring. Under stirring at 60 ° C., 452.90 g (5.00 mol) of methallyl chloride was added dropwise over 2 hours, followed by reaction at 70 ° C. for 4 hours. The yield of ethylene glycol monomethallyl ether at the end of the reaction was 82.0 mol%. The total yield of ethylene glycol monomethallyl ether based on the total amount of ethylene glycol charged from Production Example 17 was 25.9 mol%.
(Moisture loss process / solid-liquid separation process)
Dehydration and filtration were carried out in the same manner as in Production Example 17 except that the operating pressure in the dehydration step was changed to 100 mmHg from the beginning to obtain 1732.34 g of filtrate and 163.14 g of cleaning liquid. The salt separated and recovered at this time was 395.11 g. As a result of analysis, the yield of ethylene glycol monomethallyl ether was 76.8 mol%, and the yield of ethylene glycol dimethallyl ether was 13.4 mol% (calculated on the basis of raw material methallyl chloride). Moreover, the residual water content was 1.16 mass%.
(Separation process)
Using the same distillation equipment as in Production Example 17, 1839.60 g of the reaction solution and the washing solution recovered in the previous step were charged into the bottom of the distillation column to purify ethylene glycol monomethallyl ether. At the beginning of distillation, 24.30 g of the aqueous layer was separated by oil-water separation of the refluxed liquid separated into two layers. Then, after the reflux rate was extracted at 20 with the distillation rate up to 3.2% as the initial fraction, the reflux ratio was changed to 10 and the main fraction was withdrawn. When the distillation rate reached 15.7% by mass, (i) total reflux for 15 minutes and (ii) 3.3 g of the liquid in the reflux tank was extracted in a short time, and the operation consisting of 38 times was repeated. Thereafter, a distillation rate of 23.6% to 32.8% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing salt (1083.69 g as a pure component) was recovered as a distillation residue. By the distillation operation, 375.40 g of a fraction containing ethylene glycol monomethallyl ether as a main component was obtained. As a result of analysis, the water content was 0.06% by mass, and the ethylene glycol dimethallyl ether content was 0.29% by mass.

Reference Production Example 1 (Production example in which the molar ratio of alkylene glycol to unsaturated halogen compound is 1)
Into a 2 L flask was charged 310.35 g (5.00 mol) of ethylene glycol, 420.83 g (NaOH 5.05 mol) of a 48% by mass aqueous sodium hydroxide solution, and 459.64 g (5.00 mol) of methallyl chloride. The reaction was carried out. As a result of the analysis, the yield of ethylene glycol monomethallyl ether at the end of the reaction was 24.6 mol%, and the yield of ethylene glycol dimethallyl ether was 26.8 mol% (calculated on the basis of raw material methallyl chloride).

Production Example 19
(First reaction process / moisture reduction process)
A 2 L flask was charged with 150.96 g (24.20 mol) of ethylene glycol and 205.08 g (5.05 mol) of flake sodium hydroxide, and the reaction was performed while changing the temperature from room temperature to 125 ° C. with a pressure of 20 mmHg. . At the same time, water was distilled by simple distillation to recover 131.31 g of the fraction.
(Second reaction step)
To the moisture-reducing composition obtained in the above step, 452.80 g (5.00 mol) of methallyl chloride was dropped over 3 hours at 65 ° C. to 70 ° C. with stirring, and then reacted at 70 ° C. for 6 hours. 2014.11g of reaction mixture containing precipitated salt was obtained.
(Solid-liquid separation process)
The slurry obtained in the previous step was filtered off using filter paper (No. 5B, 4 μm) to obtain 1729.39 g of filtrate. Furthermore, the solid on the filter paper was washed with 100.62 g (1.62 mol) of ethylene glycol, and 121.29 g of the obtained washing liquid was combined with the previous filtrate to obtain a filtrate. The salt separated and recovered at this time was 259.53 g. As a result of gas chromatographic analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 83.3 mol%, and the yield of ethylene glycol dimethallyl ether was 12.2 mol% (calculated on the basis of raw material methallyl chloride). . Further, when the residual water content was analyzed by the Karl Fischer method, it was 0.10% by mass.
(Separation process)
Using the same distillation equipment as in Production Example 17, 1728.00 g of the reaction solution and the washing solution recovered in the previous step were charged into the bottom of the distillation column to purify ethylene glycol monomethallyl ether. At the beginning of distillation, 5.68 g of water concentrate was collected from the reflux tank. Then, after the reflux ratio was extracted at 20 with the distillation rate up to 1.3% as the initial fraction, the reflux ratio was changed to 10 and the main fraction was extracted. Thereafter, the distillation rate from 23.2% to 29.1% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing salt (1153.31 g as a pure component) was recovered as a distillation residue. By the distillation operation, a fraction containing 378.63 g of ethylene glycol monomethallyl ether as a main component was obtained. As a result of analysis, the water content was 0.09% by mass, and the ethylene glycol dimethallyl ether content was 0.36% by mass.

Production Example 20
The ethylene glycol used in the first reaction step was 1489.71 g (24.00 mol), the flake sodium hydroxide was 123.20 g (3.03 mol), and 271.77 g (3.00 mol) methallyl chloride used in the second reaction step. The experiment was performed in the same manner as in Production Example 19 except that. The filtrate, washing solution and salt obtained in the solid-liquid separation step were 1648.76 g, 123.84 g and 101.10 g, respectively. When the filtrate was analyzed, the yield of ethylene glycol monomethallyl ether was 89.0 mol%, and the yield of ethylene glycol dimethallyl ether was 7.2 mol% (calculated on the basis of raw material methallyl chloride). The residual water content was 0.10% by mass.

As described above, it is shown that an unsaturated ether composition can be obtained in a high yield by reacting a polyhydric alcohol and the unsaturated halogen compound at a preferable ratio, and a recovered composition containing a polyhydric alcohol is used. It was found that the unsaturated ether composition was efficiently produced by carrying out the reaction.

FIG. 1 is a chart showing the LC analysis result of the reaction product M-1. FIG. 2 is a chart showing the LC analysis result of the reaction product M-2. FIG. 3 is a chart showing the LC analysis result of the reaction product M-3. FIG. 4 is a chart showing the LC analysis result of the reaction product M-4.

Claims (8)

A method of producing an unsaturated (poly) alkylene glycol ether monomer by addition reaction of an alkylene oxide with an unsaturated alcohol,
The production method includes a step of performing an addition reaction under the condition that 0.001 to 25 parts by mass of an unsaturated (poly) alkylene glycol diether monomer is present with respect to 100 parts by mass of the unsaturated alcohol. A method for producing an unsaturated (poly) alkylene glycol ether monomer. The unsaturated alcohol has the following general formula (1):
X- (OR) _a -OH (1)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms. OR is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. A is a number of 0 to 300; 2. The method for producing an unsaturated (poly) alkylene glycol ether monomer according to claim 1, wherein the average added mole number of the alkylene group is represented by. The unsaturated (poly) alkylene glycol diether monomer has the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; The average number of moles added of the oxyalkylene group and a number of 1 to 300.)
The unsaturated (poly) alkylene glycol ether monomer has the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents the average number of moles added of the oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) The unsaturated group according to claim 1 or 2, A method for producing a (poly) alkylene glycol ether monomer. An unsaturated alcohol composition comprising an unsaturated alcohol and an unsaturated (poly) alkylene glycol diether monomer,
The unsaturated alcohol has the following general formula (4):
X- (OR) _b -OH (4)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms; OR is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; b is a number of 1 to 300; Represents the average number of moles added of the alkylene group.)
The unsaturated (poly) alkylene glycol diether monomer has the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; It is the average number of moles added of the oxyalkylene group and is a number from 1 to 300.)
The unsaturated alcohol composition comprises 0.001 to 25 parts by mass of an unsaturated (poly) alkylene glycol diether monomer with respect to 100 parts by mass of the unsaturated alcohol. The unsaturated alcohol composition according to claim 4, wherein the unsaturated alcohol composition is obtained by reacting a halide having an unsaturated bond with (poly) alkylene glycol. A method for producing a polymer having a (poly) alkylene glycol chain by polymerizing a monomer component containing an unsaturated (poly) alkylene glycol ether monomer,
The production method is polymerized under the condition that 0.001 to 20 parts by mass of the unsaturated (poly) alkylene glycol ether monomer is contained with respect to 100 parts by mass of the unsaturated (poly) alkylene glycol ether monomer. A process for producing a polymer having a (poly) alkylene glycol chain, comprising the step of: The unsaturated (poly) alkylene glycol diether monomer has the following general formula (2):
X—O— (R ¹ O) _m —Y (2)
(Wherein X and Y are the same or different and represent an alkenyl group having 2 to 6 carbon atoms; R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; The average number of moles added of the oxyalkylene group and a number of 1 to 300.)
The unsaturated (poly) alkylene glycol ether monomer has the following general formula (3):
_{^{X-O- (R 2 O)}} n -R 3 (3)
(In the formula, X represents an alkenyl group having 2 to 6 carbon atoms, R ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is a number of 1 to 300. Represents an average number of added moles of an oxyalkylene group, and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. A method for producing a polymer having a glycol chain. A polymer having a (poly) alkylene glycol chain obtained by the production method according to claim 6 or 7.

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